U.S. patent application number 11/665668 was filed with the patent office on 2008-02-28 for flame retardant resin composition.
This patent application is currently assigned to Asahi Kasei Chemicals Corporation. Invention is credited to Fumiki Murakami, Jun-Ichi Nakahashi.
Application Number | 20080051495 11/665668 |
Document ID | / |
Family ID | 36202876 |
Filed Date | 2008-02-28 |
United States Patent
Application |
20080051495 |
Kind Code |
A1 |
Murakami; Fumiki ; et
al. |
February 28, 2008 |
Flame Retardant Resin Composition
Abstract
A flame retardant composition comprising a specific
phenolic-based resin (A) and a specific phosphor compound (B) can
be suitably used for a resin and can provide a resin composition
which is excellent in flame retardancy, thermal resistance,
moisture resistance, extrusion workability, demolding availability,
thermal stability, impact resistance, mechanical properties and the
like.
Inventors: |
Murakami; Fumiki; (Tokyo,
JP) ; Nakahashi; Jun-Ichi; (Tokyo, JP) |
Correspondence
Address: |
STAAS & HALSEY LLP
SUITE 700
1201 NEW YORK AVENUE, N.W.
WASHINGTON
DC
20005
US
|
Assignee: |
Asahi Kasei Chemicals
Corporation
Tokyo
JP
|
Family ID: |
36202876 |
Appl. No.: |
11/665668 |
Filed: |
October 13, 2005 |
PCT Filed: |
October 13, 2005 |
PCT NO: |
PCT/JP05/18838 |
371 Date: |
April 18, 2007 |
Current U.S.
Class: |
524/100 ;
524/116; 524/130; 524/133; 524/138; 524/508; 524/538; 524/539;
524/611 |
Current CPC
Class: |
C08K 5/5399 20130101;
C08L 61/06 20130101; C08L 2666/02 20130101; H05K 1/0373 20130101;
C08K 5/5399 20130101; C08L 61/06 20130101; C08L 61/06 20130101 |
Class at
Publication: |
524/100 ;
524/116; 524/130; 524/133; 524/138; 524/508; 524/538; 524/539;
524/611 |
International
Class: |
C08K 5/3492 20060101
C08K005/3492; C08F 283/08 20060101 C08F283/08; C08K 5/51 20060101
C08K005/51 |
Foreign Application Data
Date |
Code |
Application Number |
Oct 18, 2004 |
JP |
2004-303317 |
May 18, 2005 |
JP |
2005-145443 |
Claims
1. A flame retardant composition comprising: (A) a phenol-based
resin which has an area fraction (a) with a weight average
molecular weight in polystyrene equivalent of 870 or more and an
area fraction (b) with a weight average molecular weight in
polystyrene equivalent of less than 870, the area fraction (a)
being 74% or more and, 98% or less based on the total 100% of the
area fractions (a) and (b), and has a weight averagelmolecular
weight in polystyrene equivalent of 2,000 to 80,000, the weight
average molecular weight in polystyrene equivalent being measured
with a gel permeation chromatography using a tetrahydrofran as a
solvent at a column temperature of 35.degree. C. at a flow rate of
1 mL/min; and (B) a phosphor compound (excluding non-condensed
phosphoric ester).
2. The flame retardant composition according to claim 1,
characterized in that the component (A) is a novolac-type phenol
resin.
3. The flame retardant composition according to claim 1,
characterized in that the component (A) contains a tri-nuclear
complex component in an amount of 7% or less.
4. The flame retardant composition according to claim 1,
characterized in that the component (A) contains a bi-nuclear
complex component in an amount of 10% or less.
5. The flame retardant composition according to claim 1,
characterized in that the component (B) comprises at least one
member selected from the group consisting of condensed phosphoric
ester, phosphinate and phosphazene compound.
6. The flame retardant composition according to claim 1,
characterized in the component (B) comprises at least one member
selected from the group consisting of condensed phosphoric ester
and phosphazene compound.
7. The flame retardant composition according to claim 1,
characterized in that the component (B) contains at least
phosphazene compound.
8. The flame retardant composition according to claim 1,
characterized in that the component (B) comprises phosphazene
compound and a content of a cyclic trimer and/or a cyclic tetramer
is 80 wt % or more.
9. The flame retardant composition according to claim 1,
characterized in that the component (B) comprises phosphazene
compound and a content of a cyclic trimer is 76 wt % or more.
10. A flame retardant composition comprising: (A) a novolac-type
phenol-based resin which has an area fraction (a) with a weight
average molecular weight in polystyrene equivalent of 870 or more
and an area fraction (b) with a weight average molecular weight in
polystyrene equivalent of less than 870, the area fraction (a)
being 74% or more and 98% or less based on the total 100% of the
area fractions (a) and (b), has a weight average molecular weight
in polystyrene equivalent of 2,000 to 80,000, the weight average
molecular weight in polystyrene equivalent being measured with a
gel permeation chromatography using a tetrahydrofran as a solvent
at a column temperature of 35.degree. C. at a flow rate of 1
mL/min, has a content of a tri-nuclear complex composition of 7% or
less; and (B) at least one phosphor compound selected form the
group consisting of condensed phosphoric ester and phosphazene
compound.
11. The flame retardant composition according to claim 1,
characterized in that the composition further incorporates
nitrogen-containing compound.
12. The flame retardant composition according to claim 11,
characterized in that the nitrogen-containing compound is
triazine-based compound.
13. The flame retardant composition according to claim 1,
characterized in that the contents of the components (A) and (B)
are 1 to 90 parts by weight and 10 to 99 parts by weight,
respectively, relative to the total of 100 parts by weight of the
components (A) and (B).
14. The flame retardant composition according to claim 1, further
comprising a resin (C) different from the phenol-based resin
(A).
15. The resin composition according to claim 14, characterized in
that the content of the flame retardant composition (the total of
the components (A) and (B)) is 0.1 to 200 parts by weight relative
to 100 parts by weight of the resin (C).
16. The resin composition according to claim 14, characterized in
that the resin (C) comprises at least one member selected from the
group consisting of polyphenylene ether-based resin,
polystyrene-based resin, polyalkylene allylate-based resin,
polyamide-based resin, polycarbonate-based resin, polyphenylene
sulfide-based resin, polypropylene, polyethylene, ABS
(acrylonitrile butadiene styrene) resin, thermotropic liquid
crystal and polystyrene-containing elastomer.
17. The resin composition according to claim 14, characterized in
that the resin (C) comprises at least one member selected from the
group consisting of polyalkylene allylate-based resin and
polyamide-based resin.
18. A resin composition comprising polyamide resin having 5 to 75
wt % of aromatic ring component in a main chain and the flame
retardant composition according to claim 1.
19. The resin composition according to claim 14, characterized in
further comprising a filler.
20. The resin composition according to claim 19, characterized in
that the content of the filler is 1 to 200 parts by weight relative
to the total of 100 parts by weight of the components other than
the filler.
21. A molded article formed with the resin composition according to
claim 14.
22. The flame retardant composition according to claim 10,
characterized in that the component (B) is phosphazene
compound.
23. The flame retardant composition according to claim 10
characterized in that the composition further incorporate a
nitrogen containing compound.
24. A flame retardant composition comprising: (A) a novolac-type
phenol-based resin which has an area fraction (a) with a weight
average molecular weight in polystyrene equivalent of 870 or more
and an area fraction (b) with a weight average molecular weight in
polystyrene equivalent of less than 870, the area fraction (a)
being 74% or more and 98% or less based on the total 100% of the
area fractions (a) and (b), has a weight average molecular weight
in polystyrene equivalent of 2,000 to 80,000, the weight average
molecular weight in polystyrene equivalent being measured with a
gel permeation chromatography using a tetrahydrofran as a solvent
at a column temperature of 35.degree. C. at a flow rate of 1
mL/min, and has a content of a tri-nuclear complex composition of
7% or less; and (B) a phosphazene compound, and a triazine-based
compound.
25. The flame retardant composition according to claim 10,
characterized in that the contents of the components (A) and (B)
are 1 to 90 parts by weight and 10 to 99 parts by weight,
respectively, relative to the total of 100 parts by weight of the
components (A) and (B).
26. The flame retardant composition according to claim 24,
characterized in that the contents of the components (A) and (B)
are 1 to 90 parts by weight and 10 to 99 parts by weight,
respectively, relative to the total of 100 parts by weight of the
components (A) and (B).
27. The flame retardent composition according to claim 1, further
comprising a resin (C) different from the phenol-based resin
(A).
28. The flame retardent composition according to claim 1, further
comprising a resin (C) different from the phenol-based resin
(A).
29. A resin composition comprising polyamide resin having 5 to 75
wt % of aromatic ring component in a main chain and the flame
retardant composition according to claim 10.
30. A resin composition comprising polyamide resin having 5 to 75
wt % of aromatic ring component in a main chain and the flame
retardant composition according to claim 24.
Description
TECHNICAL FIELD
[0001] The present invention relates to a flame retardant
composition. More specifically, the invention relates to a flame
retardant composition excellent in processability as well as flame
retardancy, moisture resistance, thermal resistance, and extrusion
workability when it is added to resins.
BACKGROUND ART
[0002] Conventional methods for flame retardation of flammable
resins include those which comprise adding chloride-containing
compound, bromide-containing compound or antimony trioxide to
resins; and incorporating chloride-containing compound or
bromide-containing compound into resins. However, it has been said
that these methods are not preferred from the viewpoint of
environmental protection and toxicity, and improvement of flame
retarding methods has been required. As to the flame retarding
methods devoid of chloride-containing compound or
bromide-containing compound, the method using phosphorus-based
flame retardants have been investigated.
[0003] It has been said that the mechanism of flame retardation for
resins is to block heat and oxygen supply to a burning resin with a
film of polyphosphate phase formed on the resin surface during
burning and a char layer formed by dehydration of the resin. This
mechanism is considered to be particularly effective against resins
for which it is easy to form a char film, that is, easy to
dehydrate. While, for the flame retardation of a resin for which it
is hard to form a char film by dehydration with phosphorus or a
phosphor compound, an amount of phosphorus or a phosphor compound
to be incorporated into the resin needs to be increased since the
flame retardation of the resin mainly depends on a film formed by
polyphosphate phase.
[0004] For flame retardation of resins for which it is hard to form
a char film without increasing the amount of phosphorus and
phosphor compounds, it will be conceived to employ a flame
retardant resin composition incorporating a component to be a raw
material of a char film in advance.
[0005] Patent Document 3 proposes a method using a crosslinked
phosphazene compound and a polyphenylene ether resin as a flame
retardant for flame retardation of polyalkylene allylate-based
resin. The crosslinked phosphazene compound and polyphenylene ether
resin impart good flame retardancy to a polyalkylene allylate-based
resin. However, the polyalkylene allylate-based resin containing
the crosslinked phosphazene compound and polyphenylene ether resin
as a flame retardant is not sufficient enough in processability,
thermal resistance, mechanical property, dielectric characteristic,
and appearance of the molded article thereof.
[0006] There has also been disclosed an art for flame retardation
by adding a phenol resin (to the flammable resin) having a weight
average molecular weight in polystyrene equivalent of 500,000 or
more (Patent Document 4). However, the addition of such a high
molecular weight phenol resin unfavorably causes considerable
deterioration in processing flowability and effect of imparting
flame retardancy.
[0007] Further, there has been disclosed an art achieving flame
retardation without deteriorating of inherent mechanical properties
of a resin by using a novolac-type phenolic resin having a weight
average molecular weight in polystyrene equivalent of 5,000 or more
and less than 50,000 and containing unreacted phenol in an amount
of less than 0.5 wt% of (Patent Document 5). However, this art does
not teach any technical thought that a ratio of high molecular
weight component and low molecular weight component contained in
the phenol resin in a specific range suppresses lowering of thermal
resistance while maintaining excellent flame retardancy, mechanical
properties and processability, that is, it does not suggest the
present invention.
[0008] Patent Document 6 discloses a method for flame retardation
of polyalkylene terephthalate resin by using a phenol-based resin
and a phenoxyphosphazene in combination. According to this method,
however, it is not possible to impart to a resin flame retardancy,
thermal resistance, impact strength, moldability (appearance) and
mechanical strength in good balance since a full investigation
about phenol-based resins has not been made.
[0009] These references do not lead to the effects attained by the
present inventors, namely, the effects that a flame retardant resin
comprising specific phenol resins and phosphate compounds maintain
or improve not only flame retardancy but also various properties
such as thermal resistance, mechanical property, workability, and
low smoke evolution in good balance. It was the present invention
to achieve the excellent effects as described hereinafter.
[0010] Patent Document 1: Japanese Patent Publication No.
3-73590
[0011] Patent Document 2: Japanese Patent Application Laid-Open No.
8-225714
[0012] Patent Document 3: International Publication No. WO
03/002666
[0013] Patent Document 4: Japanese Patent Application Laid-Open No.
2000-273132
[0014] Patent Document 5: Japanese Patent Application Laid-Open No.
2001-164256
[0015] Patent Document 6: International Publication No. WO
01/048086
DISCLOSURE OF THE INVENTION
Problems to be Solved by the Invention
[0016] An embodiment of the present invention provides a flame
retardant resin composition free from chlorine compound or bromine
compound and exhibits excellent flame retardancy, moisture
resistance, thermal resistance, dielectric property, low smoke
evolution and extruding activity when added to a flammable
resin.
Means for Solving the Problems
[0017] The present inventors made intensive studies to solve the
above-described problems. As a result, they have found that a flame
retardant resin composition can be obtained by adding a flame
retardant composition comprising (A) a specific phenol resin and
(B) a specific phosphor compound to a resin. Incorporation of the
flame retardant composition into a resin promotes formation of a
char film on the surface of the resin and imparts constant flame
retardancy to a resin for which it is otherwise hard to form a char
film on the surface, and further provides a flame retardant resin
composition which is excellent in thermal resistance, moisture
resistance, thermal stability, impact resistance, mechanical
property and extrusion workability and produces a molded article
with good appearance. The present invention has been achieved on
the basis of these findings.
[0018] That is, the present invention relates to: [0019] 1. A flame
retardant composition comprising:
[0020] (A) a phenol-based resin which has an area fraction (a) with
a weight average molecular weight in polystyrene equivalent of 870
or more and an area fraction (b) with a weight average molecular
weight in polystyrene equivalent of less than 870, the area
fraction (a) being 74% or more and 98% or less based on the total
100% of the area fractions (a) and (b), and has a weight average
molecular weight in polystyrene equivalent of 2,000 to 80,000, the
weight average molecular weight in polystyrene equivalent being
measured with a gel permeation chromatography using a
tetrahydrofran as a solvent at a column temperature of 35.degree.
C. at a flow rate of 1 mL/min; and
[0021] (B) a phosphor compound (excluding non-condensed phosphoric
ester). [0022] 2. The flame retardant composition according to the
above 1, characterized in that the component (A) is a novolac-type
phenol resin. [0023] 3. The flame retardant composition according
to the above 1 or 2, characterized in that the component (A)
contains a tri-nuclear complex component in an amount of 7% or
less. [0024] 4. The flame retardant composition according to any
one of the above 1 to 3, characterized in that the component (A)
contains a bi-nuclear complex component in an amount of 10% or
less. [0025] 5. The flame retardant composition according to any
one of the above 1 to 4, characterized in that the component (B)
comprises at least one selected from the group consisting of
condensed phosphoric ester, phosphinate and phosphazene compound.
[0026] 6. The flame retardant composition according to any one of
the above 1 to 4, characterized in that the component (B) comprises
at least one member selected from the group consisting of condensed
phosphoric ester and phosphazene compound. [0027] 7. The flame
retardant composition according to any one of the above 1 to 4,
characterized in that the component (B) contains at least
phosphazene compound. [0028] 8. The flame retardant composition
according to any one of the above 1 to 4, characterized in that the
component (B) comprises a phosphazene compound and a content of a
cyclic trimer and/or a cyclic tetramer is in 80 wt % or more.
[0029] 9. The flame retardant composition according to any one of
the above 1 to 4, characterized in that the component (B) comprises
a phosphazene compound and a content of a cyclic trimer is 76 wt %
or more. [0030] 10. A flame retardant composition comprising:
[0031] (A) a novolac-type phenol-based resin having a content of a
tri-nuclear complex composition of 7% or less and a weight average
molecular weight in polystyrene equivalent of 2,000 to 80,000;
and
[0032] (B) at least one phosphor compound selected form the group
consisting of a condensed phosphoric ester and a phosphazene
compound. [0033] 11. The flame retardant composition according to
any one of the above 1 to 10, characterized in that the composition
further incorporates a nitrogen-containing compound. [0034] 12. The
flame retardant composition according to the above 11,
characterized in that the nitrogen-containing compound is a
triazine-based compound. [0035] 13. The flame retardant composition
according to the above 1 to 12, characterized in that the contents
of the components (A) and (B) are 1 to 90 parts by weight and 10 to
99 parts by weight, respectively, relative to the total of 100
parts by weight of the components (A) and (B). [0036] 14. The resin
composition comprising a resin (C) and the flame retardant
composition according to any one of the above 1 to 13. [0037] 15.
The resin composition according to the above 14, characterized in
that the content of the flame retardant composition (the total of
the components (A) and (B)) is 0.1 to 200 parts by weight relative
to 100 parts by weight of the resin (C). [0038] 16. The resin
composition according to the above 14 or 15, characterized in that
the resin (C) comprises at least one selected from the group
consisting of polyphenylene ether-based resin, polystyrene-based
resin, polyalkylene allylate-based resin, polyamide-based resin,
polycarbonate-based resin, polyphenylene sulfide-based resin,
polypropylene, polyethylene, ABS (acrylonitrile butadiene styrene)
resin, thermotropic liquid crystal and polystyrene-containing
elastomer. [0039] 17. The resin composition according to the above
14 or 15, characterized in that the resin (C) comprises at least
one selected from the group consisting of polyalkylene
allylate-based resin and polyamide-based resin. [0040] 18. A resin
composition comprising polyamide resin having 5 to 75 wt % of
aromatic,ring component in a main chain and the flame retardant
composition according to any one of the above 1 to 13. [0041] 19.
The resin composition according to any one of the above 14 to 18,
characterized in further comprising a filler. [0042] 20. The resin
composition according to the above 19, characterized in that the
content of the filler is 1 to 200 parts by weight relative to the
total of 100 parts by weight of the components other than the
filler. [0043] 21. A molded article formed with the resin
composition according to any one of the above 14 to 20. Advantages
of the Invention
[0044] A flame retardant composition comprising a specific
phenol-based resin (A) and a specific phosphor compound (B)
provides a resin composition which exhibits excellent flame
retardancy, thermal resistance, moisture resistance, extrusion
workability, mold releasability, thermal stability, impact
resistance, mechanical properties and the like especially when
added to a resin.
Best Mode for Carrying Out the Invention
[0045] The present invention will be explained in detail below.
[0046] In an embodiment of the present invention, (A) a specific
phenol-based resin and (B) a specific phosphor compound are
essential components. A flame retardant composition prepared by
appropriately combining these components the flame retardant resin
composition facilitates development of a char layer upon heating at
a high temperature and imparts excellent flame retardancy and
mechanical properties to a resin composition together with good
appearance to a molded article formed with the resin composition
even when it is added to a resin in a small amount.
(A) Phenol-Based Resin
[0047] In an embodiment of the present invention, the combination
of a phenol-based resin and component (B) of phosphor compound
generates a synergetic effect and imparts excellent flame
retardancy, thermal resistance, mechanical properties to the resin
composition, and further imparts good appearance to a molded
article formed therewith. The phenol-based resin used in the
present invention has an area fraction (a) with a weight average
molecular weight in polystyrene equivalent of 870 or more and an
area fraction (b) with a weight average molecular weight in
polystyrene equivalent of less than 870, which are measured with a
gel permeation chromatography (GPC) by using a tetrahydrofran as a
solvent at a column temperature of 35.degree. C. at a flow rate of
1 mL/min, and the proportion of the area fraction (a) is 74% to
98%, preferably 74% to 95%, more preferably 74% to 92% based on the
total 100% of the area fractions (a) and (b).
[0048] In view of the balance of flame retardancy, thermal
resistance, processability and the like, a phenol-based resin
preferably used is such that contains a tri-nuclear complex
exhibiting peak top around a retention time of 10.0 to 10.1
minutes, which is measured by GPC using a tetrahydrofran as a
solvent in proportion of 7% or less, preferably 5% or less, more
preferably 4% or less, further preferably 3% or less.
[0049] In an embodiment of the present invention, a phenol-based
resin satisfying the above mentioned conditions, namely, a
phenol-based resin having an area fraction (a) in proportion of 74%
or more and 98% or less based on the total 100% of the area
fraction (a) at a retention time of 6.1 to 9.7 minutes and the area
fraction (b) at a retention time of 9.7 to 11.9 minutes, which are
measured with a GPC using a tetrahydrofran as a solvent at a column
temperature of 35.degree. C. at a flow rate of 1 mL/min, imparts
excellent flame retardancy, thermal resistance, mechanical
properties, processability and the like to the resin composition
and good appearance to a molded article formed with the resin
composition thereof, and especially enhances flame retardancy
synergically. The proportion of the area fraction (a) is preferably
74% or more and 95% or less, more preferably 74% or more and 92% or
less, most preferably 74% or more and 90% or less.
[0050] The measurement of the area fraction of a phenol-based resin
with a GPC is conducted using Waters Alliance (manufactured by
Nihon Waters K.K.) under the conditions of a tetrahydrofran
solvent, a column temperature of 35.degree. C. and a flow rate of 1
mL/min. For the column, Waters Styragel HR1, HR3 and HR4
(manufactured by Nihon Waters K.K.) are connected in series. As a
detector, UV (Waters 2487; wavelength: 254 nm) and/or RI (Waters
2414) are used. The area fraction at a retention time of 6.1 to 9.7
minutes and 9.7 to 11.9 minutes is calculated by the following
process. When area enclosed by the GPC chart baseline, the GPC
curve at 6.1 to 9.7 minutes and a vertical line drawn from the GPC
curve to the GPC chart baseline at a retention time of 9.7 minutes
is regarded as area (a'), and the area enclosed by the GPC chart
baseline, the GPC curve at 9.7 to 11.9 minutes and a vertical line
drawn from the GPC curve to the GPC chart baseline at a retention
time of 11.9 minutes is regarded as area (b'), the percentage of
(a') relative to the total of (a') and (b') is regarded as an area
fraction (a) and that of (b') is as an area fraction (b). A
calibration curve is prepared using standard polystyrene. A
molecular weight at a retention time of 9.7 minutes calculated on
the basis of the calibration curve was about 870.
[0051] Further, the content of the tri-nuclear complex is measured
as follows. A peak exhibiting its peak top at around a retention
time of 10.0 to 10.1 minutes is regarded as a peak of the
tri-nuclear complex with a GPC under the above mentioned condition.
The area (S1), which is encompassed with a straight line vertically
drawn down from a point showing the lowest absorbance value (Bottom
1) between the peak of the tri-nuclear complex and a peak
exhibiting its top peak at around a retention time of 9.8 minutes,
a straight line vertically drawn down from a point showing the
lowest absorbance value (Bottom 2) between the peak of the
tri-nuclear complex and a peak exhibiting its top peak around a
retention time of 10.4 minutes, the base line and the GPC curve, is
divided with the area (the whole area S2), which is encompassed
with the GPC curve and the base line in a retention time of 6.1 to
11.9 minutes, and further is multiplied by 100 to obtain a peak
area fraction (%) of the tri-nuclear complex. The thus-obtained
value is regarded as a content of the tri-nuclear complex. Peaks
exhibiting its peak top at around a retention time of 10.4 to 10.7
minutes are regarded as a peak of the bi-nuclear complex and at
around a retention time of 11.1 to 11.3 minutes are regarded as a
peak of a free monomer, respectively, and the each area fraction is
calculated. The obtained area fraction of each component is
regarded as its content.
[0052] As the phenol-based resin used in the present invention, any
phenol resin can be used so long as it has conventionally known
structures. The examples of the phenol resins include but are not
limited to novolac-type phenol-based resin, resol-type phenol-based
resin, phenol aralkyl-based resin, polyvinyl phenol-based resin,
and the like. These resins can be modified with cashew, oil, rubber
or the like. Of these, in view of a balance in flame retardancy
imparting effects, production cost and the like, novolac-type
phenol-based resin can be particularly preferably used.
[0053] A production method for a novolac-type phenol-based resin
preferably used in accordamce with an embodiment of the present
invention is not particularly limited so long as it does not exceed
the range of the present invention. In general, the resin can be
obtained by addition condensation of phenols and aldehydes in the
presence or absence of an acid catalyst.
[0054] A resol-type phenol-based resin can be obtained by addition
condensation of phenols and aldehydes in the presence of a basic
catalyst.
[0055] The phenols suitably used may include phenols with
substituted with an alkyl groups of 0 to 12 carbon atoms such as
phenol, cresol, xylenol, ethyl phenol, propyl phenol, bisphenol A,
bisphenol F, butylphenol, pentyl phenol, alkylphenol, and resorcin.
Moreover, the aldehydes suitably used may include formaldehyde,
acetaldehyde, propyl aldehyde, and benzenes having formyl
group.
[0056] An acid catalyst which can be used for condensation reaction
of phenols and aldehydes is not particularly limited. For example,
hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid,
toluene sulfonic acid and the like are preferably used.
[0057] A phenol-based resin used in the present invention
preferably has a weight average molecular weight in polystyrene
equivalent of 2,000 to 80,000, more preferably 2,000 to 50,000,
further preferably 3,000 to 50,000, especially preferably 3,000 to
30,000 from the viewpoint of a balance in flame retardancy
imparting effects, mechanical properties, processability and
workability.
[0058] From the viewpoint of molding flowability, mechanical
properties, low smoke evolution and the like, it is preferable that
the phenol-based resin used in an embodiment of the present
invention preferably contains a bi-nuclear complex in a smaller
amount. Specifically, the content of the bi-nuclear complex
measured according to the GPC of the bi-nuclear complex and free
monomer described in Examples of the present invention is
preferably 10% or less in an area fraction. Considering the problem
caused by the bleeding upon extrusion or molding, a phenol-based
resin with a content of the free monomer is 5% or less, preferably
3% or less is suitably used. Further, if higher flame retardancy,
molding flowability, mechanical properties, thermal stability,
workability and the like are required, a phenol-based resin with
the total content of a free monomer, bi-nuclear complex and
tri-nuclear complex of 17.5% or less, more preferably 17.0% or
less, further more preferably 16.5% or less is suitably used.
[0059] The production method of the above phenol-based resins are
not limited. An example thereof includes the methods disclosed in
Japanese Patent Application Laid-Open No. 2004-323822 and Japanese
Patent Application Laid-Open No. 11-246643.
(B) Phosphor Compound
[0060] In an embodiment of the present invention, any known
phosphor compound other than non-condensed phosphoric esters are
preferably used. Examples of the phosphor compounds include
condensed phosphate ester, phosphazene compound, phosphinate,
phosphonate, phosphate ester amid, phosphorised polymer, phosphinic
oxide, phosphinic sulfide, tertiary phosphinics such as triaryl
phosphine, trialkyl phosphine, bis(diarylphosphino)benzene and
tris(diarylphosphino)benzene, and the like. These compounds may be
used singly or in combination. Non-condensed phosphate such as
triphenylphosphate or tricresylphosphate is not preferable because
it unfavorably exhibits poor workability and processability when
combined with a specific phenol resin (A).
(B-1) Phosphazene Compound
[0061] As the phosphazene compound suitably used in an embodiment
of the present invention, various known compounds can be used. A
structure of the phosphazene compounds suitably used in an
embodiment of the present invention is described, for example, in
"Inorganic Polymers", 1992 p 61-p 140, James E. Mark, Harry R.
Allcock, and Robert West, Pretice-Hall International, Inc. For
instance, the compounds include cyclic phosphazene compounds
represented by the following formula (1) and/or chain phosphazene
compounds represented by the following formula (2). ##STR1## Among
them, phosphazene compounds having the above structures in an
amount of 95 wt % is preferred.
[0062] In the above formulas, n is an integer of 3-25, m is an
integer of 3-10,000, and a substituent X is at least one
substituent selected from the group consisting of an alkyl group of
1-6 carbon atoms, an aryl group of 6-11 carbon atoms, a fluorine
atom, an aryloxy group having a substituent represented by the
following formula (3), a naphthyloxy group, and an alkoxy group or
alkoxy-substituted alkoxy group of 1-6 carbon atoms. ##STR2##
(wherein Y.sub.1, Y.sub.2, Y.sub.3, Y.sub.4 and Y.sub.5 represent
at least one substituent selected from the group consisting of a
hydrogen atom, a fluorine atom, an alkyl group or alkoxy group of
1-5 carbon atoms, phenyl group and a group containing a hetero
atom.) One or more or all of the hydrogen atoms on the substituent
may be substituted with fluorine. Y in the above formula represents
--N.dbd.P(O) (X) or --N.dbd.P (X).sub.3, and Z represents
--P(X).sub.4 or --P(O) (X).sub.2.
[0063] These compounds may be used singly or in combination.
[0064] One of the factors used for determining flame retardancy is
the concentration of phosphorus atoms contained in a molecule of
the phosphazene compound. In the phosphazene compounds, chain
phosphazene compounds with a chain structure have substituents at
molecular ends such that phosphorus content thereof is lower than
cyclic phosphazene compounds. In the case that the phosphazene
compound and the cyclic phosphazene compound are added in the same
amount, it is considered that the cyclic phosphazene compounds more
effectively impart flame retardancy than the chain phosphazene
compounds. Accordingly, in an embodiment of the present invention,
the phosphazene compound with cyclic structure are preferably
employed. In addition, the phosphor compound containing the cyclic
phosphazene composition in an amount of 95 wt % or more is
preferable.
[0065] The substituent X in the phosphazene compound is not
particularly limited. The substituent X includes, for example,
alkyl groups such as methyl group, ethyl group, n-propyl group,
isopropyl group, n-butyl group, s-butyl group, tert-butyl group,
n-amyl group, and isoamyl group; [0066] aryl groups such as phenyl
group, 2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl
group, 2,6-dimethylphenyl group, 3,5-dimethylphenyl group,
2,5-dimethylphenyl group, 2,4-dimethylphenyl group,
3,4-dimethylphenyl group, 4-tert-butylphenyl group, and
2-methyl-4-tert-butylphenyl group; [0067] alkoxy groups such as
methoxy group, ethoxy group, n-propyloxy group, isopropyloxy group,
n-butyloxy group, tert-butyloxy group, s-butyloxy group, n-amyloxy
group, isoamyloxy group, tert-amyloxy group, and n-hexyloxy group;
[0068] alkoxy substituted alkoxy group such as methoxy methoxy
group, methoxy ethoxy group, methoxy ethoxy methoxy group, methoxy
ethoxy ethoxy group, and methoxy propyloxy group; [0069] alkyl
substituted phenoxy group such as phenoxy group, 2-methylphenoxy
group, 3-methylphenoxy group, 4-methylphenoxy group,
2,6-dimethylphenoxy group, 2,5-dimethylphenoxy group,
2,4-dimethylphenoxy group, 3,5-dimethylphenoxy group,
3,4-dimethylphenoxy group, 2,3,4-trimethylphenoxy group,
2,3,5-trimethylphenoxy group, 2,3,6-trimethylphenoxy group,
2,4,6-trimethylphenoxy group, 2,4,5-trimethylphenoxy group,
3,4,5-trimethylphenoxy group, 2-ethylphenoxy group, 3-ethylphenoxy
group, 4-ethylphenoxy group, 2,6-diethylphenoxy group,
2,5-diethylphenoxy group, 2,4-diethylphenoxy group,
3,5-diethylphenoxy group, 3,4-diethylphenoxy group,
4-n-propylphenoxy group, 4-isopropyl phenoxy group,
4-tert-butylphenoxy group, 2-methyl-4-tert-butylphenoxy group,
2-phenylphenoxy group, 3-phenylphenoxy group, and 4-phenylphenoxy
group; [0070] aryl substituted phenoxy group; naphthyl group;
naphthyloxy group; and the like. The hydrogen contained in a part
or the whole of these groups may be substituted with groups
containing fluorine and/or hetero atoms. The group containing
hetero atoms herein indicates groups containing B, N, O, Si, P, S
atoms. For example, there can be exemplified amino group, amide
group, aldehyde group, glycidyl group, carboxyl group, hydroxide
group, mercapto group, silyl group, and the like.
[0071] Further, these phosphazene compounds may be crosslinked with
a crosslinking group selected from the group consisting of
phenylene group, biphenylene group and groups represented by the
formula (4) according to the technology disclosed in International
Publication No. WO00/09518. ##STR3## (wherein X represents
--C(CH.sub.3).sub.2--, --SO.sub.2--, --S-- or --O--, and y
represents 0 or 1.) These phosphazene compounds with crosslinked
structures may be specifically produced by reacting a
dichlorophosphazene oligomer with an alkali metal salt of phenol
and an alkali metal salt of an aromatic dihydroxy compound. These
alkali metal salts are added to the dichlorophosphazene oligomer in
an amount slightly exceeding a theoretical amount.
[0072] These phosphazene compounds may be used singly or in
combination.
[0073] Furthermore, the phosphazene compound may be a mixture of
phosphazene compounds having different structures, i.e., cyclic
phosphazene compounds such as cyclic trimers and cyclic tetramers,
and chain phosphazene compound. Processability of a resin
composition incorporating the phosphazene compound tends to be more
preferable as the contents of cyclic trimers and cyclic tetramers
increase. Specifically, the preferred phosphazene compounds contain
cyclic trimer and/or tetramer compounds in an amount of 80 wt % or
more, preferably 85 wt % or more, more preferably 93 wt % or more.
Further, when the phosphazene compound is used in combination with
a phenol resin specified in an embodiment of the present invention,
using the phosphazene compound with a trimer content of 70 wt % or
more, preferably 76 wt % or more, more preferably 80 wt % or more,
is effective to impart excellent flame retardancy and to improve
mechanical properties.
[0074] Depending on a kind or structure of substituents, the
phosphazene compound can take various forms such as liquid, wax and
solid. It may be in any form so long as the effects of the present
invention are not damaged. A phosphazene compound in a solid form
may have a bulk density of not lower than 0.45 g/cm.sup.3,
preferably not lower than 0.45 g/cm.sup.3 and not higher than 0.75
g /cm.sup.3.
[0075] Each of the contents of alkali metal components such as
sodium and potassium in the phosphazene compound is preferably 200
ppm or less, more preferably 50 ppm or less, and further more
preferably the total content of alkali metal components is 50 ppm
or less. In addition, it is desired that the content of the
phosphazene compound in which at least one of the substituents X in
the formula (1) is a hydroxyl group, namely, the phosphazene
compound containing a P--OH bond, is less than 1 wt %, and that the
content of chlorine is 1000 ppm or less, preferably 500 ppm or
less, more preferably 300 ppm or less based on the total weight of
the phosphazene compound.
[0076] The phosphazene compound in which at least one of the
substituents X is a hydroxyl group can have an oxo structure
represented by the following formula (5). It is desired that the
content of the oxo compound is less than 1 wt % in the phosphazene
compound as well as the content of the phosphazene compound
containing a hydroxyl group. The same can be applied to the
phosphazene compound having a chain structure represented by the
above formula (2). ##STR4## (wherein a+b=n; n is integer of 3 or
more; and X is an aryloxy group and/or an alkoxy group and they may
independently be the same or different from each other.) (B-2)
Condensed Phosphoric Ester
[0077] As the condensed phosphoric ester suitable in an embodiment
of the present invention, various conventional compounds can be
used. One of the examples is pentaerythritol diphosphate or
phosphoric ester compounds having the following formula (6) or (7).
##STR5## (wherein Q.sub.1, Q.sub.2, Q.sub.3, Q.sub.4, Q.sub.9,
Q.sub.10, Q.sub.11 and Q.sub.12 independently represent a hydrogen
atom or an alkyl group of 1 to 6 carbon atoms; Q.sub.5, Q.sub.6,
Q.sub.7, Q.sub.8 and Q.sub.13 independently represent a hydrogen
atom or the methyl group; m1, m2, m3, m4, m7, m8, m9 and m10
independently represent an integer from 0 to 3; m5 and m6
independently represent an integer from 0 to 2; and m11
independently represents an integer from 0 to 4.) (B-3)
Phosphinate
[0078] A phosphinate which can be used in an embodiment of the
present invention includes at least one selected from the group
consisting of a phosphinate represented by the following formula
(8) and/or (9), and/or the polymers thereof. ##STR6## (wherein
Q.sub.1, Q.sub.2, Q.sub.3 and Q.sub.4 represent a hydrogen atom or
an alkyl group of 1 to 12 carbon atoms, an alkoxy group of 1 to 12
carbon atoms, an aryl group, and an aryloxy group; Q.sub.5
represents at least one group of 1-18 carbon atoms selected from
alkylene, aryl alkylene, arylene, alkyl arylene and diarylene; n
and m are each an integer of 1-3; x is an integer of 1 or 2; and M
represents at least one group selected from a metal atom, an amide,
an ammonium group and a melamine derivative, which belong to after
the fourth cycle of the periodic table.) (B-4) Tertiary
Phosphines
[0079] As the tertiary phosphines that can be used in an embodiment
of the present invention, any conventional compounds can be
suitably used. From the viewpoint of the balance of thermal
resistance, flame retardancy and mechanical properties, 10% weight
loss temperature during heating from room temperature to
600.degree. C. at a heating rate of 10.degree. C./min in an inert
gas atmosphere according to the TGA measurement, is preferably 150
to 320.degree. C. An example of such tertiary phosphines includes
triarylphosphine, trialkylphosphine, triaryloxyphosphine and
trialkoxyphosphine. More specifically, among them,
triarylphosphines represented by the following formula (10) are
suitably used. ##STR7## (wherein T.sub.1, T.sub.2, T.sub.3 and
T.sub.4 independently represent a hydrogen atom or an alkyl or aryl
group of 1 to 12 carbon atoms; T.sub.5 represents a hydrogen atom
or a methyl group; m1, m2, m3 and m4 independently represent an
integer of 0 to 5; m5 independently represents an integer of 0 to
4; and n represents an integer of 0 to 3. As an aryl group, a
naphthyl group can be also suitably used, and the three aryl groups
bonded to the phosphorus atom may be all the same group or
independently different from one another.)
[0080] The water content of phosphor compound (B) suitably used in
an embodiment of the present invention is 1000 ppm or less,
preferably 800 ppm or less, more preferably 650 ppm or less,
furthermore preferably 500 ppm or less, still more preferably 300
ppm or less from the viewpoint of dielectric property, hydrolysis
resistance and the like. When it is especially necessary to take
into consideration properties such as heat stability upon kneading
the phosphor compound with a resin or an effect of imparting flame
retardancy, the acid value measured based on JIS K6751 is 1.0 or
less, preferably 0.5 or less, more preferably 0.3 or less,
particularly preferably 0.1 or less.
[0081] The component (B) suitably used in an embodiment of the
present invention has a solubility to water of 1000 ppm or less,
preferably 500 ppm or less, more preferably 100 ppm or less,
further preferably 50 ppm or less, most preferably 25 ppm or less
from the viewpoint of hydrolysis resistance and moisture
resistance. The solubility to water indicates an amount of a sample
dissolved in water when a sample is mixed with distilled water at a
concentration of 0.1 g/ml and stirred for an hour at a room
temperature.
[0082] From the viewpoint of flame retardancy, low smoke evolution
during burning, low volatility and the like, which are exhibited
upon the use with the component (A), the specific phosphor compound
in an embodiment of the present invention advantageously has a
temperature difference between 50% weight loss temperature and 5%
weight loss temperature of 20 to 150.degree. C., preferably 20 to
120.degree. C. The weight loss temperature is measured by
thermogravimetric analysis (TGA) wherein a sample is heated in an
inert gas atmosphere from a room temperature to 600.degree. C. at a
heating rate of 10.degree. C./min. Moreover, when the phosphor
compound is mixed with a resin, the 50% loss in weight temperature
is preferably 320 to 500.degree. C., more preferably 350 to
460.degree. C. from the viewpoint of incombustion efficiency
achieved by prompt forming of a char layer during burning.
[0083] Depending on the kinds and structures of substituents
contained therein, the phosphor compound suitably used in
embodiments of the present invention can take various forms such as
liquid, wax, solid and the like. Any suitable forms can be used so
long as the effects of embodiment of the present invention are not
damaged.
[0084] When it is necessary to consider the thermal resistance of a
phosphor compound itself and its low volatility, condensed
phosphoric ester, phosphinate and phosphazene compound are suitably
used among the phosphor compounds suitably used in an embodiment of
the present invention. Preferably used are condensed phosphoric
ester synthesized using bisphenol A and phenol as raw materials,
condensed phosphoric ester obtained using bisphenol A or resorcin
and 2,6-xylenol as raw materials, and phosphazene compound.
Moreover, when hydrolysis resistance is further required to be
considered, cyclic phosphazene compounds are especially suitably
used.
(Mixing Ratio of Flame Retardant Composition)
[0085] The mixing ratio of flame retardant composition is not
particularly limited so long as the effects of embodiments of the
present invention can be achieved. To achieve the effects of
embodiments of the present invention effectively, the mixing ratio
of the component (A) and the component (B) is composed so that the
amount of the component (A) is 1 to 90 parts by weight and the
component (B) is 99 to 10 parts by weight relative to 100 parts by
weight of the sum of the component (A) and the component (B).
Preferably, the amount of the component (A) is 3 to 80 parts by
weight and the component (B) is 97 to 20 parts by weight, more
preferably the amount of the component (A) is 10 to 80 parts by
weight and the component (B) is 90 to 20 parts by weight.
(Shape of Flame Retardant Composition)
[0086] The shape of flame retardant composition is not particularly
limited so long as the effects of embodiments of the present
invention can be achieved. The flame retardant composition is
supplied, for example, as a powder, tablets, pellets, blocks, wax,
liquid, an oil and the like. Moreover, in the flame retardant
composition of the present invention, each component may be
completely dissolved with or within each other or simply mixed with
one another. Further, the composition can be a mixture of the
dissolved component and the simply mixed component.
(Use of Flame Retardant Composition)
[0087] The flame retardant composition of embodiments of the
present invention can be suitably used in a wide variety of fields,
and the method and field of the use are not particularly limited.
An example of suitable methods of use includes flame retardants for
a resin, rubbers, lubricants, lithium ion batteries, solar
batteries, fuel cells, noncompatible electrolytes, battery
electrical equipments, demolding agents, demolding film, grooving
materials, water-repellents and the like.
(Resin)
[0088] The flame retardant composition of embodiments of the
present invention can be used in combination with conventional
resins. There is no limitation on the resins to be with the
composition of the present invention. Any conventional
thermoplastic resins and curable resins are suitably used. Such
thermoplastic resins include, for example, polycarbonate-based
resin, polyphenylene ether-based resin, polyphenylene sulfide-based
resin, polypropylene-based resin, polyethylene-based resin,
polystyrene-based resin, high-impact polystyrene, elastomer
containing polystyrene, syndioctactic polystyrene-based resin,
ABS-based resin, AS-based resin, biodegradable resin,
polycarbonate-ABS resin alloy, polyalkylene allylate-based resin
such as polybutylene terephthalate, polyethylene terephthalate,
polypropylene terephthalate, polytrimethylene terephthalate,
polyethylene naphthalate and polybutylene naphthalate,
polyamide-based resin, thermotropic liquid crystal,
polyketone-based resin, and the like. In particular, polyphenylene
ether-based resin, polystyrene-based resin, ABS-based resin,
polycarbonate-based resin, polyamide-based resin, polyalkylene
allylate-based resin, alloy of polyphenylene ether and polystyrene,
alloy of polyphenylene ether and polyamide, alloy of polyphenylene
ether and thermotropic liquid crystal and alloy of polyphenylene
ether and polyphenylene sulfide are suitably used.
[0089] The curable resins include unsaturated polyester resin,
vinyl ester resin, diallyl phthalate resin, epoxy resin, cyanate
resin, xylene resin, triazine resin, urea rein, melamine resin,
benzoguanamine resin, urethane resin, oxetane resin, ketone resin,
alkide resin, furane resin, styryl pyridine resin, silicon resin,
and synthetic rubber. In particular, the epoxy resins are suitably
used. The resins used in embodiments of the present invention may
be used alone or in combination.
(Polyamide-Based Resin)
[0090] As the polyamide-based resin used in embodiments of the
present invention, a conventional resin is suitably used and there
is no particular limitation thereon.
[0091] Monomers used to synthesize the polyamide resins include, as
amines, hexamethylene diamine, pentamethylene diamine,
2-methylpentamethylene diamine, octamethylene diamine,
2-methyloctamethylene diamine, nonamethylene diamine, decamethylene
diamine, undecamethylen diamine, dodecamethylene diamine,
methaxylilene diamine, 2,2,4-trimethyl-1,6-hexane diamine,
2,4,4-trimethyl-1,6-hexane diamine, 2,4-diethyl-1,6-hexane diamine,
2,2-dimethyl-1,7-heptane diamine, 2,3-dimethyl-1,7-heptane diamine,
2,4-dimethyl-1,7-heptane diamine, 2,5-dimethyl-1,7-heptane diamine,
2-methyl-1,8-octane diamine, 3-methyl-1,8-octane diamine,
4-methyl-1,8-octane diamine, 1,3-dimethyl-1,8-octane diamine,
1,4-dimethyl-1,8-octane diamine, 2,4-dimethyl-1,8-octane diamine,
3,4-dimethyl-1,8-octane diamine, 4,5-dimethyl-1,8-octane diamine,
2,2-dimethyl,1,8-octane diamine, 3,3-dimethyl-1,8-octane diamine,
4,4-dimethyl-1,8-octane diamine, 5-methyl-1,9-nonane diamine,
isophorone diamine, norbornane dimethylamine, tricyclodecane
dimethylamine, and the like. Of these, one or two more types of
amines can be used. Further, there can be suitably used, as
dicarboxylic acid, adipic acid, octamethylene dicarboxylic acid,
malonic acid, succinic acid, glutaric acid, pimelic acid, suberic
acid, azelaic acid, sebacic acid, dodecane dicarboxylic acid,
dimethyl malonic acid, 3,3-diethyl succinic acid, 2,2-dimethyl
glutaric acid, 2-methyl adipic acid, trimethyl adipic acid,
1,3-cyclopentane dicarboxylic acid, 1,4-cyclohexane dicarboxylic
acid, terephthalic acid, isophthalic acid, 2,6-naphthalene
dicarboxylic acid, 2,7-natphthalene dicaroxylic acid,
1,4-naphthalene dicarboxylic acid, 1,4-phenylenedioxy diacetic
acid, 1,3-phenylenedioxy diacetic acid, diphenic acid,
4,4'-biphenyl dicarboxylic acid, 4,4'-oxydibenzoic acid,
diphenylmethane-4,4'-dicarboxylic acid,
diphenylsulfone-4,4'-dicarboxylic acid, decamethylene dicarboxylic
acid, undecamethylene dicarboxylic acid, dodecamethylene
dicarboxylic acid, and the like; as amino acid, pentamethylene
amino carboxylic acid, decamethylene amino carboxylic acid,
undecamethylene amino carboxylic acid, and the like may be used;
and as lactams, caprolactam, laurolactam, and the like may be used.
These monomers can be used alone or in combination.
[0092] The polyamide-based resins obtained by the combination of
the above monomers include polyamide 6, polyamide 66, polyamide
66/6, polyamide 46, polyamide 610, polyamide 612, polyamide 11,
polyamide 12, polyamide 6I, polyamide 6T, polyamide 9T, polyamide
MXD6, polyamide 66/6I, polyamide 66/6T, polyamide 6T/6I, polyamide
66/6I/6, polyamide 66/6I/11, polyamide 66/6I/12, polyamide
66/6I/610, polyamide 66/6I/612, polyamide 10T, polyamide 12T, and
the like. These polyamide-based resins can be used in alone or in
combination.
[0093] A polymerization method of the polyamide-based resin is not
particularly limited so long as the method is a general
polymerization method of an polyamide. Ordinarily, when the
polyamide-based resin is polymerized by a diamine and a
dicarboxylic acid, a condensation polymerization reaction is
carried out by preparing an equivalent salt of an amine and an acid
or adding an amine and an acid separately in an equivalent amount.
When the polyamide-based resin is polymerized from a lactam, the
condensation polymerization is carried out by adding a small amount
of water, amino acid, mineral acid or the like as a ring-opening
catalyst. A melt polymerization, in which a polymerization is
proceeded with heating a monomer or a monomer solution to remove a
water, is used widely in industry. It is well known to add an amine
or an acid as a controlling agent of polymerization degree during
the polymerization. Further, the polymerization method also
includes a method comprising the steps of heating a monomer in the
presence of water in a closed vessel to pre-polymerize an oligomer
and post-polymerizing the pre-polymerized oligomer in a kneader or
an extruder. Depending of types of a monomer, a method wherein a
monomer is polymerized with a kneader or an extruder without
pre-polymerization of an oligomer can be exemplified.
[0094] When the polyamide of the present invention is produced,
there can be added phosphoric acid, phosphorous acid,
hypophosphorous acid, or salts or esters thereof as a catalyst. The
above salts or esters include salts of phosphoric acid, phosphorous
acid or hypophosphorous acid and metal salts such as potassium,
sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin,
tungsten, germanium, titanium, and antimony; ammonium salt of
phosphoric acid, phosphorous acid or hypophosphorous acid; and
ethyl ester, isopropylester, butyl ester, hexyl ester, isodecyl
ester, octadecyl ester, decyl ester, stearyl ester, and phenyl
ester of phosphoric acid, phosphorous acid or hypophosphorous
acid.
[0095] In an embodiment of the present invention, when it is
necessary to impart flame retardancy especially effectively and
also to impart flowability in good balance, the polyamide-based
resin having an aromatic ring component in a main chain at a
content of 5 to 75 wt %, preferably 25 to 65 wt %, more preferably
31 to 55 wt %, is suitably used. The content of an aromatic ring
component is obtained by the general equation (1). Content of
aromatic ring component (,,)=(total atomic weight of carbon and
hydrogen composing aromatic ring)/(total atomic weight of repeat
unit of polyamide).times.100(%) Equation (1)
[0096] When the polyamide is a copolyamide, the content is obtained
by the general equation (2). Content of aromatic ring component
(,,)=,, ,,i.times..alpha.i.times.100(%) Equation (2) [0097] ,,i:
content of aromatic ring component of i-th copolyamide component
[0098] ,,i: weight fraction of i-th copolyamide component relative
to total weight of polyamide
[0099] The polyamide used in embodiments of the present invention
preferably has a polymerization degree, that is, a relative
viscosity, in the specific range. The preferable relative viscosity
of a semiaromatic polyamide measured according to JIS K 6810 in 98%
sulfuric acid at a concentration of 1% at a temperature of
25.degree. C. is 1.5 to 4.0, preferably 1.8 to 3.0. The polyamide
is desirable to have an appropriate relative viscosity from the
viewpoint of material strength, flowability, moldability,
appearance of a molded article, and the like.
[0100] The end of the polyamide of embodiments of the present
invention may be capped. The end-capping agent is not particularly
limited so long as it is a monofunctional compound which is
reactive to an amino group or a carboxyl group at a polyamide end.
The end sealing agent includes an acid anhydride such as
monocarboxylic acid, monoamine and phthalic anhydride,
monoisocyanate, mono-acid halide, monoesters, monoalcohols, and the
like. From the viewpoint of reactivity stability of capped
terminals or the like, monocarboxylic acid or monoamine is
preferable. More preferred is a monocarboxylic acid from the view
point of easy handling, toxicity or the like.
[0101] Monocarboxylic acids to be used as an end-capping agent are
not particularly limited as long as they are reactive with amino
groups. For example, there can be exemplified aliphatic
monocarboxylic acid such as acetic acid, propionic acid, butyric
acid, valeric acid, caproic acid, caprylic acid, lauric acid,
tridecyl acid, myristic acid, palmitic acid, stearic acid, pivalic
acid, and isobutyric acid; alicyclic monocarboxylic acid such as
cyclohexane carboxylic acid; aromatic carboxylic acid such as
benzoic acid, toluic acid, .alpha.-naphthalene carboxylic acid,
.beta.-naphthalene carboxylic acid, methylnaphthalene carboxylic
acid, and phenylacetic acid. These monocarboxylic acids can be used
alone or in combination. Of these, from the viewpoint of
reactivity, stability of capped terminals, cost, and the like,
acetic acid, propionic acid, butyric acid, valeric acid, caproic
acid, caprylic acid, lauric acid, tridecyl acid, myristic acid,
palmitic acid, stearic acid and benzoic acid are preferred.
[0102] Monoamines to be used as an end-capping agent are not
particularly limited as long as they are reactive with carboxylic
groups. The monoamines includes, for example, alphatic monoamines
such as methylamine, ethylamine, propylamine, butylamine,
hexylamine, octylamine, decylamine, stearyl amine, dimethyl amine,
diethylamine, dipropylamine, and dibutyl amine; alicyclic
monoamines such as cyclohexylamine and dicyclohexylamine; aromatic
monoamines such as aniline, toluidine, diphenylamine and
naphthylamine; and the like. These monoamines can be used alone or
in combination. Of these, from the viewpoint of reactivity, high
boiling point, stability of capped terminals, cost and the like,
butylamine, hexylamine, octylamine, decylamine, stearyl amine,
cyclohexylamine, and aniline are preferred.
(C-2) Polyalkylene Allylate-Based Resin
[0103] As the polyalkylene allylate-based resins, the conventional
resins are suitably employed. They includes, for example,
polyethylene terephthalate, polypropylene terephthalate,
polybutylene terephthalate, polytrimethylene terephthalate,
polyethylene naphthalate, polypropylene naphthalate, polybutylene
naphthalate, poly-1,4-cyclohexane dimethylene terephthalate, and
the like.
[0104] The polyalkylenearylate-based resin used in embodiments of
the present invention can be obtained by a well known method such
as a direct esterification or transesterification using an alkylene
glycol and an aromatic dicarboxylic acid or an ester thereof (for
instance, terephthalic acid, dimethyl terephthalate, isophthalic
acid as a copolymerization element and dimethyl isophthalate).
[0105] These polyalkylenearylate-based resins can be used singly or
in combination.
(C-3) Polyphenylene Ether-Based Resin
[0106] The polyphenylene ether-based resin suitably used in
embodiments of the present invention is preferably a homopolymer or
a copolymer having a repeat unit represented by the general formula
(11) and/or (12). ##STR8## (wherein R.sub.1, R.sub.2, R.sub.3,
R.sub.4, R.sub.5 and R.sub.6 independently represent an alkyl group
of 1-4 carbon atoms, an aryl group and halogen; with the proviso
that R.sub.5 and R.sub.6 cannot simultaneously be hydrogen.)
[0107] Representative examples of homopolymer of polyphenylene
ether resins include poly(2,6-dimethyl-1,4-phenylene)ether,
poly(2-methyl-6-ethyl-14-phenylene)ether,
poly(2,6-diethyl-1,4-phenylene)ether,
poly(2-ethyl-6-n-propyl-1,4-phenylene)ether,
poly(2,6-di-n-propyl-1,4-phenylene)ether,
poly(2-methyl-6-n-butyl-1,4-phneylene)ether,
poly(2-ethyl-6-isopropyl-1,4-phenylene)ether,
poly(2-methyl-6-hydroxyethyl-1,4-phenylene)ether, and the like.
[0108] Among them, poly(2,6-dimethyl-1,4-phenylene) ether is
preferred. Especially preferred is polyphenylene ethers disclosed
in Japanese Patent Application Laid-Open No. 63-301222, which
contain, as a partial structure,
2-(dialkylaminomethyl)-6-methylphenylene ether units,
2-(N-alkyl-N-phenylaminomethyl)-6-methylphenylene ether units or
the like.
[0109] The polyphenylene ether copolymers are copolymers having a
phenylene ether structure as the main monomer unit. Examples of the
copolymers include copolymer of 2,6-dimethylphenol and
2,3,6-trimethylphenol; copolymer of 2,6-dimethylphenol and
o-cresol; copolymer of 2,6-dimethylphenol, 2,3,6-trimethylphenol
and o-cresol; copolymer of 2,6-dimethylphenol and bisphenol
represented by the following general formula (13); and the like.
##STR9## (wherein R.sub.7, R.sub.8, R.sub.9 and R.sub.10
independently represent an alkyl group of 1-4 carbon atoms, an aryl
group or hydrogen; X represents --C(CH.sub.3).sub.2--,
--SO.sub.2--, --S-- or --O--; y represents 0 or 1; and z represents
1 or 2.)
[0110] In embodiments of the present invention, it is possible to
use a modified polyphenylene ether resin in a range where the
object of the present invention is not damaged, which is obtained
by introducing reactive functional groups such as carboxyl group,
epoxy group, amino group, mercapto group, silyl group, hydroxyl
group, anhydrous dicarboxylic group into a part or the whole of the
polyphenylene ether resin by some methods such as grafting reaction
or copolymerization. These can be used singly or in
combination.
[0111] The modified polyphenylene ether resins obtained by
modifying a part or the whole of the polyphenylene ether resin with
an unsaturated carboxylic acid or the functional derivatives
thereof are disclosed in Japanese Patent Application Laid-Open No.
2-276823, No. 63-108059 and No. 59-59724, and the like. For
instance, the modified polyphenylene ether resins can be obtained
by melt mixing a polyphenylene ether resin with an unsaturated
carboxylic acid or a functional derivative thereof to react in the
presence or absence of a radical initiator. Alternatively, the
modified resins may be produced by dissolving a polyphenylene ether
and an unsaturated carboxylic acid or a functional derivative
thereof in an organic solvent in the presence or absence of a
radical initiator and reacting them in a solution.
[0112] Examples of the unsaturated carboxylic acids or functional
derivatives thereof include dicarboxylic acid such as maleic acid,
fumaric acid, itaconic acid, halogenated maleic acid,
cis-4-cyclohexene-1,2-dicarboxylic acid and
endo-cis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid and the
like; acid anhydrides, esters, amides, imides and the like of these
carboxylic acids; monocarboxylic acid such as acrylic acid and
methacrylic acid and esters, amides and the like of monocarboxylic
acid. Moreover, there can be used a saturated carboxylic acid that
pyrolytically decomposes itself at a reaction temperature upon
production of a modified polyphenylene ether to form functional
derivatives used in embodiments of the present invention.
Specifically, maleic acid and citric acid are exemplified. These
may be used alone or in combination.
[0113] The molecular weight of polyphenylene ether which can be
used in embodiments of the present invention is not particularly
limited so long as the effects of the one or more embodiments of
the present invention are not damaged. Concretely, the
polyphenylene ether having a number average molecular weight of 500
to 30,000 is preferably used. In the case that a composition
particularly excellent in molding processability is required,
polyphenylene ether having a number average molecular weight of 500
or more and 5,000 or less, preferably 1,200 or more and 4,000 or
less is suitably employed. In the case that a composition
particularly excellent in thermal resistance is required, one
having a number average molecular weight over 5,000 is suitably
employed. According to a property that is especially required as a
resin composition, polyphenylene ether having a suitable molecular
weight is appropriately employed.
(C-4) Polycarbonate Resin
[0114] A polycarbonate resin preferably used in the present
invention is a polymer having a repeat unit represented by the
following general formula (14). ##STR10## (wherein Ar represents
bivalent aromatic-containing group of 4-200 carbon atoms such as
phenylene, biphenylene, terphenylene, naphthylene and a group
represented by the following general formula (15). ##STR11##
(wherein X represents --O--, --S--, --C(O)--, --C(O)O--, --C(O)NH--
and a group represented by the following general formula (16) or
(17). ##STR12## wherein R.sub.11, R.sub.12, R.sub.13, R.sub.14,
R.sub.15 and R.sub.16 each independently represent hydrogen atom,
an alkyl group of 1-20 carbon atoms or an aryl group, and the
hydrogen atom in the substituted group may be substituted by a
fluorine atom.)
[0115] Moreover, a polycarbonate resin suitably used in embodiments
of the present invention may have a branch structure. In addition,
a polyorganosiloxane modified polycarbonate-based resin modified
with an organosiloxane (for instance, the resin disclosed in such
as Japanese Patent Application Laid-Open No. 6-100684 and No.
10-182832) is suitably used, too. These may be used alone or in
combination.
[0116] A terminal group of a polycarbonate resin is not
particularly limited so long as the effects of one or more
embodiments of the present invention is achieved. Examples of such
terminal groups include alkyl groups, alkyl carbonate groups, aryl
groups, aryl carbonate groups and the like. These groups can bond
more than a kind of groups as a terminal group.
[0117] The molecular weight of a polycarbonate resin which is
suitably used in embodiments of the present invention is not
particularly limited so long as the effects of one or more
embodiments of the present invention is not damaged. Concretely,
for example, there is suitably used a polycarbonate resin having a
number average molecular weight in polystyrene equivalent of 1,000
to 100,000, preferably 2,000 to 70,000, more preferably 5,000 to
25,000. According to a property that is especially required as a
resin composition, a polycarbonate resin having a suitable
molecular weight may be appropriately employed.
[0118] The polycarbonate resin suitably used in embodiments of the
present invention may be produced according to various conventional
methods, and the methods are not particularly limited. For example,
a plycarbonate resin produced according to phosgene processes or
transesterification method is suitably employed.
(C-5) Thermotropic Liquid Crystal
[0119] Any thermotropic liquid crystal conventionally known can be
used widely as a thermotropic liquid crystal suitably used in
embodiments of the present invention, and they are not particularly
limited. An example thereof includes a thermotropic liquid crystal
polyester having p-hydroxybenzoic acid and ethylene terephthalate
as a main constituent unit, a thermotropic liquid crystal polyester
having p-hydroxybenzoic acid and 2-hydroxy-6-naphthoic acid as a
main constituent unit, a thermotropic liquid crystal polyester
having p-hydroxybenzoic acid, 4,4'-hydroxybiphenyl and terephthalic
acid as a main constituent unit, and the like. No particular
limitation is given.
[0120] A thermotropic liquid crystal suitably used in embodiments
of the present invention can introduce, as needed, a constituent
unit generated from other aromatic dicarboxylic acid, aromatic diol
or aromatic hydroxycarboxylic acid in a small amount which does not
damage the features and effects of one or more embodiments of the
present invention.
[0121] A temperature beginning to show the liquid crystalline state
while melting the thermotropic liquid crystal of the present
invention (hereinafter called a liquid crystal onset temperature)
is preferably 150-350.degree. C., more preferably 180-320.degree.
C. By controlling the liquid crystal onset temperature in this
range, the obtained resin composition exhibits preferable tone and
a good balance in thermal resistance and molding
processability.
[0122] An apparent melt viscosity of the thermotropic liquid
crystal suitably used in embodiments of the present invention
(liquid crystal onset temperature: +30.degree. C.; shear rate:
100/sec) is not particularly limited so long as the effects of one
or more embodiments of the present invention can be obtained. When
flowability is especially required, the melt viscosity of the
thermotropic liquid crystal is preferably 10 to 3,000 Pas, more
preferably 10-2,000 Pas, particularly preferably 10-1,000 Pas.
(Mixing Ratio)
[0123] A mixing ratio of the flame retardant composition of
embodiments of the present invention and a resin is not
particularly limited so long as the effects of one or more
embodiments of the present invention can be obtained. It is
preferable to incorporate 0.1 to 200 parts by weight of a flame
retardant composition of the components (A) and (B) relative to 100
parts by weight of the resin component (C). The component (B) is
incorporated in an amount of more preferably 1 to 150 parts,
furthermore preferably 5 to 120 parts by weight, relative to 100
parts by weight of the resin component (C).
(Nitrogen-Based Compound)
[0124] To the flame retardant composition and flame retardant resin
composition of embodiments of the present invention, a
nitrogen-containing compound may be further added to enhance the
effect of imparting flame retardancy to the flame retardant resin
composition containing the specific phenol resin and the phosphor
compound (B).
[0125] There can be exemplified tertiary amines or quaternary
ammonium salt such as triaryl amine, dialkyl arylamine, and alkyl
diaryl amine; melamine, melam, melem, mellon, methylene dimelamine,
ethylene dimelamine, decamethylene dimelamine, 1,3-cyclohexyl
dimelamine, 4,4'-diethylene dimelamine, diethylene tirmelamine,
benzoguanamine, dibenzoguanamine, succinoguanamine,
methylguanamine, acetoguanamine, melamine resin, and cyanuric acid
salt, sulfate, phosphate and organoboronate of the above
components; and triazine compounds such as
2-dibutylamino-4,6-dimercapto-S-triazine,
2-N-phenylamino-4,6-dimercapto-S-triazine,
2,4,6-trimercapto-S-triazine, triallyl cyanurate and trimethallyl
isocyanurate. When thermal resistance is especially required,
triazine-based compounds can be suitably used. Further, when
thermostability, volatile resistance or the like is required, there
is suitably used melamine condensate such as melam, melem and
mellon; or reactants of the above triazine-based compounds and
cyanuric acid, especially melamine cyanurate which is a reactant of
melamine and cyanuric acid. Moreover, one or more a part or all of
the hydrogen groups and/or amino groups of the reactant of
triazine-based compound and cyanuric acid may be substituted by the
substituents.
[0126] The production method of melamine condensate such as melam,
melem and mellon suitably used in embodiments of the present
invention is not particularly limited. For example, melamine
condensate can be obtained by heating melamine or melamine salt in
an inert gas atmosphere or under vacuum with or without an organic
acid catalyst at 280 to 320.degree. C. to conduct
self-condensation.
[0127] A melamine cyanurate preferably used in embodiments of the
present invention is an equimolar reactant of a melamine and a
cyanuric acid. For example, the melamine cyanurate can be obtained
as a white solid by agitating and mixing a melamine aqueous
solution and a cyanuric acid aqueous solution at a temperature of
about 90 to 100.degree. C., and precipitating and filtering
products obtained by the reaction. The solid is preferably ground
into fine powder for use. The above nitrogen-containing compound
can be used alone or in combination. Further, these compounds need
not be completely pure, and may contain a small amount of
unreactants.
[0128] An amount of a nitrogen-based compound added is not limited
so long as it is added in such an amount that the effects of one or
more embodiments of the present invention can be achieved. The
nitrogen-based compounds is preferably added in an amount of 1 to
200 parts by weight, more preferably 5 to 150 parts by weight,
further preferably 10 to 120 parts by weight, relative to 100 parts
by weight of the sum of the component (A) and the component
(B).
(Other Flame Retardants and Flame Retardant Auxiliary)
[0129] To the flame retardant composition and flame retardant resin
composition of embodiments of the present invention, conventionally
known flame retardants or flame retardant auxiliary such as
non-halogen or non antimony can be used together in such a range as
the effects of one or more embodiments of the present invention can
be achieved. For further improvement of flame retardancy, there can
be added for instance metal hydroxide such as magnesium hydroxide,
aluminum hydroxide, calcium hydroxide and calcium aluminate;
boron-containing compounds such as boric acid and zinc borate
compounds; silicon-containing compounds such as polyorganosiloxane,
silsesquioxane and silicon resin; and inorganic silicon compound
such as silica, kaolin clay, talc and wollastonite.
(Filler)
[0130] Moreover, conventionally known fillers can be mixed into the
flame retardant composition and flame retardant resin composition
of embodiments of the present invention in order to improve various
characteristics such as mechanical properties. The fillers include
silica, kaolin clay, talc, mica, wollastonite, titanium oxide,
glass bead, glass flake, glass fiber, calcium carbonate, barium
carbonate, calcium sulfate, barium sulfate, calcium silicate,
potassium titanate, aluminum borate, magnesium borate, fibrous
reinforcing agent such as kenaf fiber, carbon fiber, silica fiber
and alumina fiber quartz fiber, and non-fibrous reinforcing agent.
These fillers may be used alone or in combination. Further, they
may be coated with an organic or inorganic substance.
[0131] Moreover, when glass fiber is used as a filler, an
appropriate fiber is selected from long-fiber roving, short-fiber
chopped strands, milled fiber and the like. It is preferable to use
a glass fiber, of which surface is treated so as to suit a resin to
be used.
[0132] Incorporating a filler, the strength of a non-flammable
layer (or a char layer) formed during combustion can be further
improved. The layer once formed during combustion is difficult to
break and shows a stable heat insulating ability, resulting in
higher effect in flame retardancy. Further, high stiffness is
imparted to the material.
[0133] The amount of a filler mixed is not particularly limited so
long as the effects of one or more embodiments of the present
invention can be achieved. To achieve the above effects owing to
incorporation of a filler effectively, the filler is mixed in an
amount of 1-200 parts by weight, preferably 3-150 parts by weight,
more preferably 5-120 parts by weight, particularly preferably
10-100 parts by weight, relative to 100 parts by weight of the sum
of other than the filler.
(Other Additives)
[0134] When the flame retardant composition and the resin
composition comprising the flame retardant compositions of
embodiments of the present invention are used, there may be
preliminarily added other additives in such a range as the effects
of the present invention are not damaged in order to impart other
characteristics such as stiffness or dimensional stability. The
additives include stabilizers such as plasticizers, antioxidants
and ultraviolet absorbers, light stabilizer, hardeners, hardening
accelerators, antistatic agents, electroconductive agents, stress
relaxing agents, releasing agents, crystallization accelerant,
hydrolysis restrainer, lubricant, impact imparting agents, slide
modifier, compatibilizer, nucleanting agent, strengthening agent,
reinforcing agent, flow control agents, dyes, sensitizing agents,
pigments for coloration, rubber-like polymers, elecroconductive
polymers.
(Mixing Method)
[0135] The methods for mixing the flame retardant composition with
the thermoplastic resin is not particularly limited so long as the
effects of one or more embodiments of the present invention can be
achieved. For instance, they can be mixed using kneading machines
such as extruders, heating rolls, kneaders and Banbury mixers.
Among them, melt kneading by an extruder is preferred from the
viewpoint of productivity. The temperature of melt kneading may be
determined in accordance with a preferred processing temperature of
a base resin. A kneading temperature is 140 to 360.degree. C.,
preferably 180 to 320.degree. C. as a standard.
[0136] A molded article of the composition of embodiments of the
present invention can be molded by well known methods such as
injection molding, sheet molding, blow molding, injection blow
molding, inflation molding, extrusion molding, expansion molding
and film molding, and also by fabricating molding method such as
pneumatic molding and vacuum molding.
[0137] Incorporation of a curable resin may be conducted according
to a method comprising mixing components used to prepare the resin
composition without a solvent or, if necessary, mixing the
components with a solvent capable of uniformly mixing them and
removing the solvent, to obtain a resin mixture; casting the
mixture into a mold to harden followed by cooling; and taking out
the resultant molded article from the mold. Alternatively, the
resin mixture can be cast into a mold and hardened by a hot press.
The solvents for dissolving each component are not particularly
limited so long as they can uniformly mix each material and do not
damage the effects of one or more embodiments of the present
invention. Examples of the solvents include, for example, toluene,
xylene, acetone, methyl ethyl ketone, diethyl ketone,
cyclopentanone, cyclohexanone, dimethylformamide, methyl
cellosolve, methanol, ethanol, n-propanol, iso-propanol, n-butanol,
n-pentanol, n-hexanol, cyclohexanol, n-hexane and n-pentane.
[0138] In addition, there can be also exemplified a method
comprising producing the resin composition by kneading using a
kneading machine such as a heating roll, a kneader, a Banbury mixer
or an extruder, and then cooling and grinding the resulting
composition, followed by molding such as transfer molding,
injection molding, compression molding, or the like. The curing
method varies depending on the hardener used, but is not
particularly limited. For example, heat hardening, light hardening,
UV hardening, pressure hardening, moisture hardening, and the like
can be mentioned. The curing methods are not limited so long as the
effects of the present invention can be attained. The order of
mixing the components is not particularly limited so long as the
method can attain the effects of one or more embodiments of the
present invention. As the method for producing the resin
composition, there may be employed a preferred method depending on
the suitability for the resin used.
(Usage of Flame Resistance Resin Composition Thing)
[0139] The flame retardant resin compositions prepared using the
flame retardant composition of embodiments of the present invention
are suitably usable for electric and electronic parts such as coil
bobbins, fly-back transformers, connectors and deflecting yokes;
electric and electronic materials such as printed wiring boards,
printed circuit boards, sealers, electrical insulating materials,
electrical coating agents, laminated sheets, varnishes for high
speed operation, front composite materials, electric wires, aerial
materials, cables and high performance molding materials; paints,
adhesives, coating materials, tableware, buttons, fiber and paper
treating agents, decorative laminates, UV hardening inks, sealants,
synthetic leathers, thermal insulating cushioning materials,
coating film waterproofing materials, corrosion preventing linings,
binders for mold; modifying materials for lacquers, paints and
inks; resin modifying materials, aircraft interior parts, matrixes
for composite materials, utensils, OA equipment, AV equipment,
battery equipment, lighting fixtures, automobile parts, housings,
ETC, ITC, portable telephones, etc.
EXAMPLES
Embodiments of the present invention will be explained specifically
by the following examples, which should not be construed as
limiting the invention in any manner.
(1) GPC Measurement of Phenol Resin
(1-1) Measurement of Ratio of High Molecular Weight Phenol Resin
and Low Molecular Weight Phenol Resin
[0140] The measurement of the area fraction of a phenol-based resin
with a GPC is conducted using Waters Alliance (manufactured by
Nihon Waters K.K.) under the conditions of a hydrofran solvent, a
column temperature of 35.degree. C. and a flow rate of 1 mL/min.
For the column, Waters Styragel HR1, HR3 and HR4 (manufactured by
Nihon Waters K.K.) are connected in series. As a detector, UV
(Waters 2487; wavelength: 254 nm) and/or RI (Waters 2414) are used.
The area fraction at a retention time of 6.1 to 9.7 minutes and 9.7
to 11.9 minutes is calculated by the following process. When area
enclosed by the GPC chart baseline, the GPC curve at 6.1 to 9.7
minutes and a vertical line drawn from the GPC curve to the GPC
chart baseline at a retention time of 9.7 minutes is regarded as
area (a'), and the area enclosed by the GPC chart baseline, the GPC
curve at 9.7 to 11.9 minutes and a vertical line drawn from the GPC
curve to the GPC chart baseline at a retention time of 11.9 minutes
is regarded as area (b'), the percentage of (a') in relative to the
total of (a') and (b') is regarded as an area fraction (a) and that
of (b') is as an area fraction (b). A calibration curve is prepared
using standard polystyrene. A molecular weight at a retention time
of 9.7 minutes calculated on the basis of the calibration curve was
about 870.
(1-2) Measurement of Content of Tri-Nuclear Complex, Bi-Nuclear
Complex and Free Monomer
[0141] Further, the content of the tri-nuclear complex is measured
as follows. A peak exhibiting its peak top at around a retention
time of 10.0 to 10.1 minutes is regarded as a peak of the
tri-nuclear complex with a GPC under the above mentioned condition.
The area (S1), which is encompassed with a straight line vertically
drawn down from a point showing the lowest absorbance value (Bottom
1) between the peak of the tri-nuclear complex and a peak
exhibiting its top peak at around a retention time of 9.8 minutes,
a straight line vertically drawn down from a point showing the
lowest absorbance value (Bottom 2) between the peak of the
tri-nuclear complex and a peak exhibiting its top peak around a
retention time of 10.4 minutes, the base line and the GPC curve, is
divided with the area (the whole area S2), which is encompassed
with the GPC curve and the base line in a retention time of 6.1 to
11.9 minutes, and further is multiplied by 100 to obtain a peak
area fraction (%) of the tri-nuclear complex. The thus-obtained
valued is regarded as a content of the tri-nuclear complex. Peaks
exhibiting its peak top at around a retention time of 10.4 to 10.7
minutes are regarded as a peak of the bi-nuclear complex and at
around a retention time of 11.1 to 11.3 minutes are regarded as a
peak of a free monomer, respectively, and the each area fraction is
calculated. The obtained area fraction of each component is
regarded as its content.
(1-3) Weight Average Molecular Weight in Polystyrene Equivalent
[0142] The weight average molecular weight in polystyrene
equivalent was measured with a GPC under the foregoing
conditions.
(2) Flame Retardancy
[0143] The flame retardancy was measured on an injection molded
test piece having a thickness of about 0.8 mm, about 1.6 mm or
about 3.2 mm in accordance with UL-94 vertical flame test, and an
average combustion time was obtained when the test piece was
allowed to contact flames ten times. Evaluation was conducted on
whether or not an absorbent cotton caught fire due to drop the
materials during the firing.
(3) Thermal Resistance (DTUL)
[0144] The thermal resistance was measured in accordance with
ASTM-D-648 on a test piece having a thickness of about 6.4 mm under
a load of 18.6 kg.
(4) Flexural Strength
[0145] The flexural strength was measured in accordance with
ASTM-D-790 on a test piece having a thickness of about 6.4 mm.
(5) Impact Resistance (IZOD)
[0146] The impact resistance was measured in accordance with
ASTM-D-256 on a test piece (notched) having a thickness of about
6.4 mm.
(6) Appearance of Molded Article
Examples 1 to 5 and Comparative Examples 1 to 7
[0147] Molded pieces of about 1.3 mm wide, about 13 mm long and
about 3.2 mm thick were prepared using a molding machine IS-80C
manufactured by Toshiba Machine Co., Ltd. at a screw temperature of
250.degree. C., a mold temperature of 60.degree. C., an injection
time of 10 seconds and a cure time of 15 seconds, and visually
evaluated. A molded piece thickly colored was determined as bad,
one relatively thickly colored fair, one slightly colored good.
Further, a molded piece with surface sink was evaluated as bad, and
one without surface sink good.
Examples 15 and 16 and Comparative Examples 20 to 22
[0148] Molded pieces of about 1.3 mm wide, about 13 mm long and
about 3.2 mm thick were prepared using a molding machine IS-80C
manufactured by Toshiba Machine Co., Ltd. at a screw temperature of
240.degree. C., a mold temperature of 60.degree. C., an injection
time of 10 seconds and a cure time of 15 seconds, and visually
evaluated. A molded piece thickly colored was determined as bad,
one relatively thickly colored fair, one slightly colored good.
Further, a molded piece with surface sink was evaluated as bad, and
one without surface sink good.
Example 17 and Comparative Examples 23 to 25
[0149] Molded piece of about 1.3 mm wide, about 13 mm long and
about 3.2 mm thick were prepared using a molding machine IS-80C
manufactured by Toshiba Machine Co., Ltd. at a screw temperature of
240.degree. C., a mold temperature of 60.degree. C., an injection
time of 10 seconds and a cure time of 15 seconds, and visually
evaluated. A molded piece with surface sink was evaluated as bad,
and one without surface sink good.
Examples 6 to 10 and Comparative Examples 8 to 15
[0150] Molded pieces of about 1.3 mm wide, about 13 mm long and
about 0.8 and 1.6 mm thick were prepared using a molding machine
PS-40E manufactured by Nissei Plastic Industrial Co., Ltd. at a
screw temperature of 270.degree. C., a mold temperature of
80.degree. C., an injection time of 7 seconds and a cure time of 12
seconds, and visually evaluated. A molded piece with a burn mark
was evaluated as bad, and one without a burn mark good.
Examples 11 to 14 and Comparative Examples 16 to 19
[0151] Molded pieces of about 1.3 mm wide, about 13 mm long and
about 0.8 and 1.6 mm thick were prepared using a molding machine
PS-40E manufactured by Nissei Plastic Industrial Co., Ltd. at a
screw temperature of 315.degree. C., a mold temperature of
90.degree. C., an injection time of 7 seconds and a cure time of 15
seconds, and visually evaluated. A molded piece thickly colored was
determined as bad, one relatively thickly colored fair, one
slightly colored good.
(7) Thermal Stability (Mold Deposit: MD)
Examples 6 to 10 and Comparative Examples 8 to 15
[0152] Molded pieces of about 128 mm long, about 12.8 mm wide and
about 1.6 mm thick were prepared using a molding machine PS-40E
manufactured by Nissei Plastic Industrial Co., Ltd. at a cylinder
temperature of 270.degree. C. and a mold temperature of 80.degree.
C. The surface condition of the mold after 20 shots was visually
observed.
Examples 11 to 14 and Comparative Examples 16 to 19
[0153] Molded pieces of about 128 mm long, about 12.8 mm wide,
about 1.6 mm thickness were prepared using a molding machine PS-40E
manufactured by Nissei Plastic Industrial Co., Ltd. at a cylinder
temperature of 315.degree. C. and a mold temperature of 90.degree.
C. The surface condition of the mold after 20 shots was visually
observed. The surface condition of the mold after 20 shots was
visually observed.
Example 17, Comparative Example 21 to 23
[0154] The molded piece of about 1.3 mm wide, about 13 mm long and
about 3.2 mm thick were prepared using a molding machine IS-80C
manufactured by Toshiba Machine Co., Ltd. at a screw temperature of
240.degree. C., a mold temperature of 60.degree. C., an injection
time of 10 seconds and a cure time of 15 seconds. The surface
condition of the mold after 20 shots was visually observed.
[0155] Good: Less MD observed
[0156] Poor: Much MD observed
[0157] The following components were used in Examples and
Comparative Examples.
(A) Phenol-Based Resin
[0158] (A-1) Novolac-type phenol resin: PR-50731 (manufactured by
Sumitomo Bakelite Co., Ltd.), (a) 78.0%, (b) 22.0%, Mw: 10366, free
monomers: 1.9%, bi-nuclear complex: 8.1%, tri-nuclear complex: 6.0%
[0159] (A-2) Novolac-type phenol resin: PR-55307 (manufactured by
Sumitomo Bakelite Co., Ltd.), (a) 74.9%, (b) 25.1%, Mw: 3028, free
monomers: 0%, bi-nuclear complex: 2.2%, tri-nuclear complex: 6.9%
[0160] (A-3) Novolac-type phenol resin: SP-1006N (manufactured by
Asahi Organic Chemicals Industry Co., Ltd.), (a) 80.5%, (b) 19.5%,
Mw: 7509, free monomers: 1.0%, bi-nuclear complex: 7.2%,
tri-nuclear complex: 5.9% [0161] (A-4) Novolac-type phenol resin:
PR-53195 (manufactured by Sumitomo Bakelite Co., Ltd.), (a) 73.8%,
(b) 26.2%, Mw: 3503, free monomers: 0%, bi-nuclear complex: 10.1%,
tri-nuclear complex: 7.8% [0162] (A-5) Novolac-type phenol resin:
PR-53647 (manufactured by Sumitomo Bakelite Co., Ltd.), (a) 53.9%,
(b) 46.1%, Mw: 1179, free monomers: 0%, bi-nuclear complex: 2.4%,
tri-nuclear complex: 22.5% [0163] (A-6) Novolac-type phenol resin:
Tamanoru 759 (manufactured by Arakawa Chemical Industries, Ltd.),
(a) 63.5%, (b) 36.5%, Mw: 2205, free monomers: 0%, bi-nuclear
complex: 14.1%, tri-nuclear complex: 10.0% [0164] (A-7)
Novolac-type phenol resin synthesized from phenol and
paraformaldehyde, which were used as raw materials, with 5L
autoclave according to the method described in Example 3 of
Japanese Patent Application Laid-Open No. 2000-273133: (a) 98.2%,
(b) 1.8%, Mw: 883,582, free monomers: 0%, bi-nuclear complex: 0.3%,
tri-nuclear complex: 1.1% (B) Phosphorus Compound [0165] (B-1)
Phenoxyphosphazene represented by the following formula (18)
containing 93.6 wt % of n=3, 4.0 wt % of n=4 and 2.4 wt % of
n.gtoreq.5. [0166] 5% weight loss temperature: 336.degree. C., 50%
weight loss temperature: 398.degree. C., Amount of residue at
500.degree. C.: 4.7 wt %, Acid value: 0.17, water content: 182 ppm
##STR13## [0167] (B-2) Triphenyl phosphate (TPP) [0168] (B-3)
Condensed phosphoric ester synthesized from resorcin and
2,6-xylenol, which were used as raw materials: PX-200 (manufactured
by Daihachi Chemical Industry Co., Ltd.) (Nitrogen-Based
Compound)
[0169] Melamine cyanurate (MCA C-0; manufactured by Mitsubishi
Chemical Co., Ltd.)
(C) Resin
(1) Polybutylene Terephthalate
[0170] DURANEX 2002.RTM. (manufactured by Win Tech Polymer
Ltd.)
(2) Polycarbonate Resin (PC)
[0171] Caliber.RTM. 301-10 (manufactured by Sumitomo Dow Ltd.)
(3) Acrylonitrile-Butadiene-Styrene Resin (ABS)
[0172] M8801 (manufactured by company UMG ABS Ltd.)
(4) Polyphenylene Ether (PPE)
[0173] Poly-2,6-dimethyl-1,4-phenylene ether having ,,sp/c of 0.54
measured in a chloroform solution at 30.degree. C.
(5) Polyamide Resin
(PA66)
[0174] Leona.RTM. 1300S (manufactured by Asahi Kasei Chemicals
Corp.)
(PA-MXD6)
[0175] Polyamide MXD6 resin (Reny.RTM. 6002; manufactured by
Mitsubishi Gas Chemical Company, Inc.)
(PA12T)
[0176] 664 g (4.0 mol) of terephthalic acid, 802 g (4.0 mol) of
1,12-dodecanediamine, 1.95 g (0.016 mol) of benzoic acid, 0.148 g
(0.0014 mol) of sodium hypophosphite monohydrate and 1500 g of
distilled water were charged into an autoclave having an inner
volume of 5.0 L, and the internal gas in the autoclave was
substituted with nitrogen gas. The internal temperature of the
autoclave was risen to 240.degree. C. over 1.5 hours with stirring.
At this time, the internal pressure of the autoclave was risen to
3.0 MPa. After that, the temperature of the autoclave was lowered
to 290.degree. C. by gradually discharging water vapor from the
autoclave while maintaining the internal pressure 3.0 MPa. Then,
the internal pressure was reduced to normal pressure by gradually
discharging water vapor from the autoclave over 75 minutes to
obtain a polymer from a discharge valve of the autoclave. The
resultant powdered polymer was dried in a nitrogen flow at
90.degree. C. for 24 hours. .eta.r=2.5
(PA10T)
[0177] 664 g (4.0 mol) of terephthalic acid, 690 g (4.0 mol) of
1,10-decanediamine, 2.92 g (0.024 mol) of benzoic acid, 0.135 g
(0.0013 mol) of sodium hypophosphite monohydrate and 1400 g of
distilled water were charged into an autoclave having an inner
volume of 5.0 L, and the internal gas in the autoclave was
substituted with nitrogen gas. The internal temperature of the
autoclave was risen to 260.degree. C. over 1.5 hours with stirring.
At this time, the internal pressure of the autoclave was risen to
4.0 MPa. After that, the temperature of the autoclave was lowered
to 320.degree. C. by gradually discharging water vapor from the
autoclave while maintaining the internal pressure 4.0 MPa. Then,
the internal pressure was lowered to normal pressure over 90
minutes to obtain a polymer from a discharge valve of the
autoclave. The resultant powdered polymer was dried in a nitrogen
flow at 90.degree. C. for 24 hours. .eta.r=2.6
(PA9T)
[0178] 664 g (4.0 mol) of terephthalic acid, 633 g (4.0 mol) of
1,9-nonanediamine, 2.92 g (0.024 mol) of benzoic acid, 0.13 g
(0.0012 mol) of sodium hypophosphite monohydrate and 1400 g of
distilled water were charged into a autoclave having an inner
volume of 5.0 L, and the internal gas in the autoclave was
substituted with nitrogen gas. The internal temperature of the
autoclave was risen to 260.degree. C. over 1.5 hours with stirring.
At this time, the internal pressure of the autoclave was risen to
4.0 MPa. After that, the temperature of the autoclave was lowered
to 320.degree. C. by gradually discharging water vapor from the
autoclave while maintaining the internal pressure 4.0 MPa. Then,
the internal pressure was lowered until normal pressure over 90
minutes to obtain a polymer from a discharge valve of the
autoclave. The resultant powdered polymer was dried in a nitrogen
flow at 90.degree. C. for 24 hours. The dried polymer was a yellow
solid. .eta.r=2.7, [COOH]=52 mg equivalent/kg
(6) Rubber-Reinforced Polystyrene (HIPS)
[0179] Rubber-reinforced polystyrene having a rubber content of 9%,
matrix polystyrene .eta.sp/c of 0.64, measured in a toluene
solution, and volume average particle size of 1.5 .mu.m
(7) Polystyrene (GPPS)
[0180] Polystyrene having .eta.sp/c of 0.8, measured in a toluene
solution
(8) PTFE
[0181] PTFE 6C-J (DuPont-Mitsui Fluorochemicals Co., Ltd.)
(D) Filler (Glass Fiber)
[0182] T-275 (Nippon Electric Glass Co., Ltd)
Examples 1 to 14 and Comparative Examples 1 to 19
[0183] A ZSK-25 biaxial rotation extruder (manufactured by Werner
Pfleiderer) equipped with one feed opening at upstream side and
downstream side, respectively, was used. The temperature of heating
cylinder of the extruder was adjusted to the following temperature.
Each of the components other than GF was fed from the upstream side
opening at a ratio shown in Tables 1 to 8, and GF was fed from the
downstream side opening at a ratio of Tables 1 to 8. The fed
components were melt mixed at a screw rotation speed of 300 rpm.
The resultant strands were cooled and cut to obtain resin
composition pellets. [0184] Tables 1 to 3 PBT resin: cylinder
temperature of 250.degree. C. [0185] Tables 4 to 6 PA66 resin:
cylinder temperature of 275.degree. C. [0186] Tables 7 and 8
PA9T,10T,12T resin: cylinder temperature of 315.degree. C.
[0187] Then, the resultant resin composition pellets were molded
using an injection molding machine to prepare test pieces for
physical property evaluation. Physical property tests were
conducted according to the test methods mentioned above. The test
results are shown in Tables 1 to 8. TABLE-US-00001 TABLE 1 Ex. 1
Ex. 2 Ex. 3 Ex. 4 Ex. 5 PBT wt. part 41.3 43.6 41.3 41.3 36.8 (A)
Phenol-based resin (A-1) (A-1) (A-2) (A-3) (A-2) Added amount wt.
part 14.3 12.0 14.3 14.3 13.3 (B) (B-1) wt. part 9.3 9.3 9.3 9.3 --
(B-2) wt. part -- -- -- -- -- (B-3) wt. part -- -- -- -- 13.8 GF
wt. part 30.0 30.0 30.0 30.0 30.0 MCA wt. part 4.6 4.6 4.6 4.6 4.6
PTFE wt. part 0.5 0.5 0.5 0.5 0.5 [UL-94] 1.59 mm V-0 V-0 V-0 V-0
V-0 Average combustion time sec 1.6 3.9 2.2 4.0 3.1 Maximum firing
time sec 2.5 8.2 5.7 9.6 6.3 Flexural strength kg/cm.sup.2 1458
1508 1325 1261 1266 DTUL .degree. C. 183 189 183 180 175 IZOD kg
cm/cm 4.3 4.3 4.2 4.2 4.1 Appearace of molded article Coloring good
good good good good Surface sink good good good good good
[0188] TABLE-US-00002 TABLE 2 Comp. Comp. Comp. Comp. Comp. Comp.
Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7 PBT wt. part 41.3
41.3 41.3 41.3 41.3 36.8 47.6 (A) Phenol-based resin (A-4) (A-5)
(A-6) (A-7) (A-1) (A-2) (A-1) Added amount wt. part 14.3 14.3 14.3
14.3 14.3 13.3 16.5 (B) (B-1) wt. part 9.3 9.3 9.3 9.3 -- -- --
(B-2) wt. part -- -- -- -- 9.3 13.8 -- (B-3) wt. part -- -- -- --
-- -- -- GF wt. part 30.0 30.0 30.0 30.0 30.0 30.0 30.0 MCA wt.
part 4.6 4.6 4.6 4.6 4.6 4.6 5.3 PTFE wt. part 0.5 0.5 0.5 0.5 0.5
0.5 0.6 [UL-94] 1.59 mm V-1 V out V out V out V-1 V-1 V out Av.
combustion time sec 6.9 12.5 10.4 14.8 7.4 6.4 25.2 Max. combustion
time sec 16.0 43.2 32.5 38.5 13.1 15.6 69.4 Flexural strength
kg/cm.sup.2 1174 1126 1147 1112 1328 1143 -- DTUL .degree. C. 178
170 172 202 179 170 -- IZOD kg cm/cm 4.1 3.9 3.9 1.8 4.1 4.1 --
Appearace of molded article Coloring fair fair fair poor fair fair
-- Surface sink poor poor poor good poor poor --
[0189] TABLE-US-00003 TABLE 3 Comp. Comp. Comp. Ex. 1 Ex. 3 Ex. 5
Ex. 1 Ex. 2 Ex. 4 PBT wt. part 41.3 41.3 36.8 41.3 41.3 41.3 (A)
Phenol-based resin (A-1) (A-2) (A-2) (A-4) (A-5) (A-1) Added amount
wt. part 14.3 14.3 13.3 14.3 14.3 14.3 (B) (B-1) wt. part 9.3 9.3
-- 9.3 9.3 -- (B-2) wt. part -- -- -- -- -- 9.3 (B-3) wt. part --
-- 13.8 -- -- -- GF wt. part 30.0 30.0 30.0 30.0 30.0 30.0 MCA wt.
part 4.6 4.6 4.6 4.6 4.6 4.6 PTFE wt. part 0.5 0.5 0.5 0.5 0.5 0.5
[UL-94] 0.79 mm V-0 V-0 V-1 V-1 V-2 V-1 Av. combustion time sec 3.5
3.6 3.3 6.1 13.0 8.2 Max. combustion time sec 8.4 7.4 10.1 18.4
21.7 15.2
[0190] TABLE-US-00004 TABLE 4 Comp. Ex. 6 Ex. 7 Ex. 8 Ex. 8 PA66
wt. part 41.9 41.9 41.9 41.9 (A) Phenol-based resin (A-1) (A-2)
(A-3) (A-1) Added amount wt. part 14.0 14.0 14.0 14.0 (B) (B-1) wt.
part 14.0 14.0 14.0 -- (B-2) wt. part -- -- -- 14.0 GF wt. part
25.0 25.0 25.0 25.0 MCA wt. part 4.6 4.6 4.6 4.6 PTFE wt. part 0.5
0.5 0.5 0.5 [UL-94] 0.79 mm V-0 V-0 V-1 V-2 Number of cotton
ignition 0/5 0/5 0/5 2/5 Av. combustion time sec 4.0 4.7 4.8 9.1
Max. combustion time sec 9.0 8.9 10.4 21.2 Appearace of molded
article Burn mark good good good poor Thermal stability MD good
good good poor
[0191] TABLE-US-00005 TABLE 5 Comp. Comp. Comp. Comp. Comp. Ex. 9
Ex. 10 Ex. 11 Ex. 12 Ex. 13 PA66 wt. part 41.9 41.9 41.9 41.9 41.9
(A) Phenol-based resin (A-4) (A-5) (A-6) (A-7) (A-1) Added amount
wt. part 14.0 14.0 14.0 14.0 14.0 (B) (B-1) wt. part 14.0 14.0 14.0
14.0 -- (B-2) wt. part -- -- -- -- 14.0 GF wt. part 25.0 25.0 25.0
25.0 25.0 MCA wt. part 4.6 4.6 4.6 4.6 4.6 PTFE wt. part 0.5 0.5
0.5 0.5 0.5 [UL-94] 0.79 mm V out V-2 V-2 V-2 V-2 Number of cotton
ignition 5/5 5/5 5/5 5/5 2/5 Av. combustion time sec 10.3 7.3 8.2
7.9 9.1 Max. combustion time sec 31.5 29.4 24.7 18.4 21.2 Appearace
of molded article Burn mark poor poor poor good poor Thermal
stability MD poor poor poor good poor
[0192] TABLE-US-00006 TABLE 6 Comp. Comp. Ex. 9 Ex. 10 Ex. 14 Ex.
15 PA66 wt. part 31.9 31.9 31.9 31.9 MDX6 wt. part 10 10 10 10 (A)
Phenol-based resin (A-1) (A-2) (A-4) (A-5) Added amount wt. part
14.0 14.0 14.0 14.0 (B) (B-1) wt. part 14.0 14.0 14.0 14.0 GF wt.
part 25.0 25.0 25.0 25.0 MCA wt. part 4.6 4.6 4.6 4.6 PTFE wt. part
0.5 0.5 0.5 0.5 [UL-94] 0.79 mm V-0 V-0 V-2 V-2 Number of cotton
ignition 0/5 0/5 5/5 5/5 Av. combustion time sec 1.8 3.4 5.0 7.2
Max. combustion time sec 3.5 7.2 12.1 18.7 Appearace of molded
article Burn mark good good good poor Thermal stability MD good
good poor poor
[0193] TABLE-US-00007 TABLE 7 Comp. Comp. Ex. 11 Ex. 12 Ex. 16 Ex.
13 Ex. 17 PA12T wt. part 47.9 47.9 47.9 -- -- PA10T wt. part -- --
-- 47.9 47.9 (A) Phenol-based resin (A-1) (A-2) (A-5) (A-2) (A-5)
Added amount wt. part 12.0 12.0 12.0 12.0 12.0 (B) (B-1) wt. part
10.0 10.0 10.0 10.0 10.0 (B-2) wt. part -- -- -- -- -- GF wt. part
25.0 25.0 25.0 25.0 25.0 MCA wt. part 4.6 4.6 4.6 4.6 4.6 PTFE wt.
part 0.5 0.5 0.5 0.5 0.5 [UL-94] 0.79 mm V-0 V-0 V-2 V-0 V-2 Av.
combustion time sec 1.9 3.2 6.6 3.8 6.9 Max. combustion time sec
4.4 9.1 12.6 8.2 15.2 Thermal stability MD good good poor good poor
Appearace of molded article Coloring good good fair good fair Burn
mark good good poor good poor
[0194] TABLE-US-00008 TABLE 8 Comp. Comp. Ex. 14 Ex. 18 Ex. 19 PA9T
wt. part 47.9 47.9 47.9 (A) Phenol-based resin (A-1) (A-5) (A-1)
Added amount wt. part 12.0 12.0 12.0 (B) (B-1) wt. part 10.0 10.0
-- (B-2) wt. part -- -- 10 GF wt. part 25.0 25.0 25.0 MCA wt. part
4.6 4.6 4.6 PTFE wt. part 0.5 0.5 0.5 [UL-94] 0.79 mm V-0 V-2 V out
Average firing time sec 2.5 7.4 13.2 Max. combustion time sec 6.7
14.9 32.9 Extrusion bleed good poor poor Appearace of molded
article Coloring good fair fair Burn mark good poor poor
Examples 15 to 17 and Comparative Examples 20 to 25
[0195] A ZSK-25 biaxial rotation extruder (manufactured by Werner
Pfleiderer) was used. The temperature of heating cylinder of the
extruder was adjusted to 250.degree. C. Each of the components was
fed at a ratio shown in Tables 9 and 10 and melt mixed at a screw
rotation speed of 300 rpm. The resultant strands were cooled and
cut to obtain resin composition pellets.
[0196] Then, the resultant resin composition pellets were molded
using an injection molding machine to prepare test pieces for
physical property evaluation. Physical property tests were
conducted according to the test methods mentioned above. The test
results are shown in Tables 9 and 10. TABLE-US-00009 TABLE 9 Comp.
Comp. Comp. Ex. 15 Ex. 20 Ex. 16 Ex. 21 Ex. 22 PC wt. part 80.0
80.0 80.0 80.0 80.0 ABS wt. part 20.0 20.0 20.0 20.0 20.0 (A)
Phenol-based resin (A-1) (A-5) (A-1) (A-1) (A-1) Added amount wt.
part 3.0 3.0 3.0 -- -- (B) (B-1) wt. part 8.0 8.0 8.0 8.0 -- (B-2)
wt. part -- -- -- -- 8.0 PTFE wt. part -- -- 0.5 -- 0.5 [UL-94]
3.18 mm V-0 V-1 V-0 V-1 V-1 Av. combustion time sec 4.4 8.9 3.8 6.1
10.3 Max. combustion time sec 9.2 24.3 6.5 18.2 26.3 Thermal
stability MD good good good good poor Appearace of molded article
Coloring good good good good good Surface sink good poor good good
poor
[0197] TABLE-US-00010 TABLE 10 Comp. Comp. Comp. Ex. 17 Ex. 23 Ex.
24 Ex. 25 PPE wt. part 40.0 40.0 40.0 40.0 PS wt. part 15.0 15.0
15.0 15.0 HIPS wt. part 30.0 30.0 30.0 30.0 (A) Phenol-based resin
(A-1) (A-5) (A-1) (A-1) Added amount wt. part 5.0 5.0 5.0 5.0 (B)
(B-1) wt. part 10 10 10 -- (B-2) wt. part -- -- -- 10 PTFE wt. part
-- -- -- -- [UL-94] 3.18 mm V-0 V-1 V-1 V-1 Av. combustion time sec
3.0 5.6 8.3 6.1 Max. combustion sec 6.0 12.2 15.6 18.2 DTUL
.degree. C. 99 94 105 96 IZOD kg 6.4 5.8 2.1 7.2 cm/cm Thermal
stability MD good poor good poor Appearace of molded article
Surface sink good poor good poor
[0198] Tables 1 to 10 show that a combination of phenol resin
satisfying a specific condition and phosphor compound other than
non-condensed phosphoric ester can impart excellent flame
retardancy to the resin composition. In addition, the combination
can impart thermal resistance, impact resistance, mechanical
strength, moldability and thermal resistance to the resin
composition, and provide a molded article with excellent
appearance.
INDUSTRIAL APPLICABILITY
[0199] The flame retardant composition comprising a specific
phenolic-based resin (A) and a specific phosphor compound (B)
exhibits excellent flame retardancy, thermal resistance, extrusion
workability, mold releasability, thermal stability, mechanical
properties, processability and the like, particularly when added to
a resin. Therefore, the composition is suitably usable for flame
retardant for a resin, rubber, lubricants, lithium-ion batteries,
solar batteries, fuel cells, nonflammable electrolytic solutions,
battery equipments, demolding agent, demolding film, rough grooving
materials, water-repellant medicine and the like. In addition, the
flame retardant resin compositions prepared using the flame
retardant composition of embodiments of the present invention are
suitably usable for electric and electronic parts such as coil
bobbins, fly-back transformers, connectors and deflecting yokes;
electric and electronic materials such as printed wiring boards,
printed circuit boards, sealers, electrical insulating materials,
electrical coating agents, laminated sheets, varnishes for high
speed operation, front composite materials, electric wires, aerial
materials, cables and high performance molding materials; paints,
adhesives, coating materials, tableware, buttons, fiber and paper
treating agents, decorative laminates, UV hardening inks, sealants,
synthetic leathers, thermal insulating cushioning materials,
coating film waterproofing materials, corrosion preventing linings,
binders for mold, modifying materials for lacquers, paints and
inks, resin modifying materials, aircraft interior parts, matrixes
for composite materials, utensils, OA equipment, AV equipment,
battery equipment, lighting fixtures, automobile parts, housings,
ETC, ITC, portable telephones, etc.
BRIEF DESCRIPTION OF DRAWINGS
[0200] FIG. 1 GPC spectrum of the phenol resin (A-1)
[0201] FIG. 2 GPC spectrum of the phenol resin (A-2)
[0202] FIG. 3 GPC spectrum of the phenol resin (A-4)
[0203] FIG. 4 GPC spectrum of the phenol resin (A-5)
* * * * *